Compound, light emitting material, and light emitting device

ABSTRACT

To provide an excellent light emitting material. A compound represented by the following general formula is used as the light emitting material. R is a hydrogen atom, a deuterium atom, an aryl group, or a heteroaryl group bonding via a carbon atom, Ar is an aryl group, or a heteroaryl group bonding via a carbon atom, D1 and D2 each are a donor group, and at least one is a hetero ring-condensed carbazol-9-yl group.

TECHNICAL FIELD

The present invention relates to a compound useful as a light emitting material, and a light emitting device using the compound.

BACKGROUND ART

Studies for enhancing the light emission efficiency of light emitting devices such as organic electroluminescent devices (organic EL devices) are being made actively. In particular, various kinds of efforts have been made for increasing light emission efficiency by newly developing and combining an electron transporting material and a hole transporting material to constitute an organic electroluminescent device. Among them, there are seen some studies relating to an organic electroluminescent device that utilizes a delayed fluorescent material.

A delayed fluorescent material is a material which, in an excited state, after having undergone reverse intersystem crossing from an excited triplet state to an excited singlet state, emits fluorescence when returning back from the excited singlet state to a ground state thereof. Fluorescence through the route is observed later than fluorescence from the excited singlet state directly occurring from the ground state (ordinary fluorescence), and is therefore referred to as delayed fluorescence. Here, for example, in the case where a light emitting compound is excited through carrier injection thereinto, the occurring probability of the excited singlet state and the excited triplet state is statistically 25%/75%, and therefore improvement of light emission efficiency by the fluorescence alone from the directly occurring excited singlet state is limited. On the other hand, in a delayed fluorescent material, not only the excited singlet state thereof but also the excited triplet state can be utilized for fluorescent emission through the route via the above-mentioned reverse intersystem crossing, and therefore as compared with an ordinary fluorescent material, a delayed fluorescent material can realize a higher emission efficiency.

Since such principles have been clarified, various delayed fluorescent materials have become discovered by various studies. However, every material capable of emitting delayed fluorescence is not always immediately useful as a light emitting material. Some delayed fluorescent materials are relatively less likely to undergo reverse intersystem crossing, and some delayed fluorescent materials have a long lifetime. In a high current density region, excitons may accumulate to lower emission efficiency, or in continuous long-time driving, some materials may rapidly worsen. Consequently, in fact, there are very many delayed fluorescent materials with room for improvement in point of practicability. Therefore, it is pointed out that benzonitrile compounds that are known as delayed fluorescent materials also have various problems. For example, a compound having the following structure is a material that emits delayed fluorescence (see PTL 1), but has a problem in that the lifetime of delayed fluorescence thereof is long and the device durability is insufficient.

CITATION LIST Patent Literature

-   PTL 1: WO2014/208698A1

SUMMARY OF INVENTION Technical Problem

Although it has been pointed out that such a problem has been encountered, it cannot be said that the relationship between the chemical structure and the characteristics of the delayed fluorescent material has been sufficiently elucidated. Consequently, at present, it is difficult to generalize the chemical structure of a compound useful as a light emitting material, and there are many unclear points.

Given the situation, the present inventors have made repeated studies for the purpose of providing a compound more useful as a light emitting material for light emitting devices. With that, the inventors have further made assiduous studies in order to derive and generalize a general formula of a compound more useful as a light emitting material.

Solution to Problem

As a result of further promoting assiduous studies for attaining the above-mentioned object, the present inventors have found that, among isophthalonitrile derivatives, compounds having a structure that satisfies a specific requirement are useful as a light emitting material. The present invention has been proposed on the basis of these findings, and specifically has the following constitution.

[1] A compound represented by the following general formula (1):

In the general formula (1):

R represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group bonding via a carbon atom,

Ar represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group bonding via a carbon atom,

D¹ and D² each independently represent a donor group, and at least one of them is a hetero ring-condensed carbazol-9-yl group in which the hetero ring and the carbazol can be substituted.

[2] The compound according to [1], in which the compound is represented by the following general formula (2):

[3] The compound according to [1], in which the compound is represented by the following general formula (3):

[4] The compound according to any one of [1] to [3], in which D¹ and D² are the same.

[5] The compound according to any one of [1] to [3], in which D¹ and D² are different.

[6] The compound according to any one of [1] to [5], in which the hetero ring condensed with the carbazol-9-yl group of the hetero ring-condensed carbazol-9-yl group is a substituted or unsubstituted furan ring, a substituted or unsubstituted thiophene ring, or a substituted or unsubstituted pyrrole ring, and any other ring can be further condensed with the furan ring, the thiophene ring and the pyrrole ring.

[7] The compound according to any one of [1] to [6], in which the hetero ring-condensed carbazol-9-yl group has a structure of any of the following:

In the above structures, hydrogen atoms can be substituted, with which, however, any further hetero atom is not condensed.

[8] The compound according to any one of [1] to [6], in which the hetero ring-condensed carbazol-9-yl group has a structure of any of the following:

In the above structures, hydrogen atoms can be substituted, with which, however, any further hetero atom is not condensed.

[9] The compound according to any one of [1] to [6], in which the hetero ring-condensed carbazol-9-yl group has a structure of any of the following:

In the above structures, hydrogen atoms can be substituted, with which, however, any further hetero atom is not condensed. R′ represents a hydrogen atom, a deuterium atom or a substituent.

[10] The compound according to any one of [1] to [9], in which two hetero rings selected from the group consisting of a substituted or unsubstituted furan ring, a substituted or unsubstituted thiophene ring and a substituted or unsubstituted pyrrole ring, in which any other ring can be condensed with the furan ring, the thiophene ring and the pyrrole ring, are condensed with the carbazol-9-yl group of the hetero ring-condensed carbazol-9-yl group.

[11] The compound according to any one of [1] to [10], in which the hetero ring-condensed carbazol-9-yl group has a structure with a hetero ring condensed at 1,2-positions of the carbazole ring.

[12] The compound according to any one of [1] to [10], in which the hetero ring-condensed carbazol-9-yl group has a structure with a hetero ring condensed at 2,3-positions of the carbazole ring.

[13] The compound according to any one of [1] to [10], in which the hetero ring-condensed carbazol-9-yl group has a structure with a hetero ring condensed at 3,4-positions of the carbazole ring.

[14] The compound according to any one of [1] to [13], in which R and Ar differ.

[15] The compound according to any one of [1] to [13], in which R is a hydrogen atom or a deuterium atom.

[16] The compound according to any one of [1] to [15], in which Ar is a substituted or unsubstituted phenyl group, or a substituted or unsubstituted pyridyl group.

[17] The compound according to any one of [1] to [16], which is composed of atoms selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, an oxygen atom and a sulfur atom.

[18] A light emitting material of a compound of any one of [1] to [17].

[19] A light emitting device characterized by containing a compound of any one of [1] to [17].

[20] The light emitting device according to [19], in which the light emitting device has a light emitting layer and the light emitting layer contains the above compound and a host material.

[21] The light emitting device according to [20], in which the light emitting device has a light emitting layer, the light emitting layer contains the above compound and a light emitting material, and the light emitting material mainly emits light.

Advantageous Effects of Invention

The compound of the present invention is useful as a light emitting material. Also, the compound of the present invention includes a compound having a short delayed fluorescence lifetime. Further, an organic light emitting device using the compound of the present invention has high device durability and is useful.

BRIEF DESCRIPTION OF DRAWING

FIG. 1 This is a schematic cross-sectional view showing an example of a layer configuration of an organic electroluminescent device.

DESCRIPTION OF EMBODIMENTS

The contents of the invention will be described in detail below. The constitutional elements may be described below with reference to representative embodiments and specific examples of the invention, but the invention is not limited to the embodiments and the examples. In the description herein, a numerical range expressed as “to” means a range that includes the numerical values described before and after “to” as the lower limit and the upper limit. Apart of all of the hydrogen atoms that are present in the molecule of the compound used in the invention can be substituted with a deuterium atom (²H, deuterium D). In the chemical structural formulae in the present description, a hydrogen atom is expressed as H. or the expression is omitted. For example, when the expression of the atoms bonding to the ring skeleton-constituting carbon atoms of a benzene ring is omitted, H bonds to the ring skeleton-constituting carbon atom in the site where the expression is omitted. In the chemical structural formulae in the present description, a deuterium atom is expressed as D.

Compound Represented by General Formula (1)

At least one of D¹ and D² in the general formula (1) represents a hetero ring-condensed carbazol-9-yl group. The hetero ring and the carbazole ring constituting the hetero ring-condensed carbazol-9-yl group each may be substituted or may not be substituted.

The number of the hetero ring condensed with the carbazol-9-yl group is 1 or more, preferably 1 or 2, more preferably 1. When 2 or more hetero rings are condensed, these hetero rings can be the same or different. In one embodiment of the present invention, the hetero ring is condensed at the 1,2-positions of the carbazol-9-yl group. In another embodiment of the present invention, the hetero ring is condensed at the 2,3-positions of the carbazol-9-yl group. In still another embodiment of the present invention, the hetero ring is condensed at the 3,4-positions of the carbazol-9-yl group.

The hetero ring condensed with the carbazol-9-yl group is a ring containing a hetero atom. The hetero atom is preferably selected from an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom, more preferably selected from an oxygen atom, a sulfur atom and a nitrogen atom. In one preferred embodiment, the hetero atom is an oxygen atom. In another preferred embodiment, the hetero atom is a sulfur atom. In still another preferred embodiment, the hetero atom is an nitrogen atom. The number of the hetero atom contained as a ring skeleton constituting atom of the hetero ring is 1 or more, preferably 1 to 3, more preferably 1 or 2. In one preferred embodiment, the number of the hetero atom is 1. When the number of the hetero atom is 2 or more, they are preferably hetero atoms of the same species, but may be composed of hetero atoms of different species. For example, two or more hetero atoms can be all nitrogen atoms. The other ring skeleton constituting atoms than the hetero atom are carbon atoms.

The number of the ring skeleton constituting atoms that constitute the hetero ring condensed with the carbazol-9-yl group is preferably 4 to 8, more preferably 5 to 7, even more preferably 5 or 6. In one preferred embodiment, the number of the ring skeleton constituting atoms that constitute the hetero ring is 5. Preferably, the hetero ring has 2 or more conjugated double bonds, and preferably, through condensation with the hetero ring, the conjugated system of the carbazole ring is extended (preferably having aromaticity). Preferred examples of the hetero ring include a furan ring, a thiophene ring, and a pyrrole ring.

The hetero ring condensed with the carbazol-9-yl group can be further condensed with any other ring. The ring to be condensed can be a single ring or a condensed ring. The ring to be condensed includes an aromatic hydrocarbon ring, an aromatic hetero ring, an aliphatic hydrocarbon ring and an aliphatic hetero ring. The aromatic hydrocarbon ring includes a benzene ring. The aromatic hetero ring includes a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a pyrrole ring, a pyrazole ring and an imidazole ring. The aliphatic hydrocarbon ring includes a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring. The aliphatic hetero ring includes a piperidine ring, a pyrrolidine ring, and an imidazolidine ring. Specific examples of the condensed ring include a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyran ring, a tetracene ring, an indole ring, an isoindole ring, a benzimidazole ring, a benzotriazole ring, a quinoline ring, an isoquinoline ring, a quinazoline ring, a quinoxaline ring and a cinnoline ring.

In one preferred embodiment of the present invention, the hetero ring-condensed carbazol-9-yl group is a benzofuran-condensed carbazol-9-yl group, a benzothiophene-condensed carbazol-9-yl group, an indole-condensed carbazol-9-yl group or a silaindene-condensed carbazol-9-yl group. In a more preferred embodiment of the present invention, the hetero ring-condensed carbazol-9-yl group is a benzofuran-condensed carbazol-9-yl group, a benzothiophene-condensed carbazol-9-yl group, or an indole-condensed carbazol-9-yl group.

In the present invention, as the benzofuran-condensed carbazol-9-yl group, a substituted or unsubstituted benzofuro[2,3-a]carbazol-9-yl group can be employed. Also a substituted or unsubstituted benzofuro[3,2-a]carbazol-9-yl group can be employed. Also a substituted or unsubstituted benzofuro[2,3-b]carbazol-9-yl group can be employed. Also a substituted or unsubstituted benzofuro[3,2-b]carbazol-9-yl group can be employed. Also a substituted or unsubstituted benzofuro[2,3-c]carbazol-9-yl group can be employed. Also a substituted or unsubstituted benzofuro[3,2-c]carbazol-9-yl group can be employed.

A preferred benzofuran-condensed carbazol-9-yl group is a carbazol-9-yl group in which only one benzofuran ring is condensed at 2,3-positions and any other hetero ring is not condensed (in which, however, a benzene ring can be condensed). Specifically, preferred are groups having any of the following structures, and in the following structures, the hydrogen atom can be substituted. For example, preferably exemplified are those in which a part of the hydrogen atoms in the following structure are substituted deuterium atoms, or those in which all hydrogen atoms in the following structure are substituted with deuterium atoms. Unsubstituted structures are also preferably employable.

Also preferred is a carbazol-9-yl group in which two benzofuran rings are condensed at 2,3-positions and any other hetero ring is condensed therein (in which, however, a benzene ring can be condensed). Specifically, preferred are groups having any of the following structures, and in the following structures, the hydrogen atom can be substituted. For example, preferably exemplified are those in which a part of the hydrogen atoms in the following structure are substituted with deuterium atoms, or those in which all hydrogen atoms in the following structure are substituted with deuterium atoms. Unsubstituted structures are also preferably employable.

In the present invention, as the benzothiophene-condensed carbazol-9-yl group, a substituted or unsubstituted benzothieno[2,3-a]carbazol-9-yl group is employable. Also a substituted or unsubstituted benzothieno[3,2-a]carbazol-9-yl group is employ able. Also, a substituted or unsubstituted benzothieno[2,3-b]carbazol-9-yl group is employable. Also a substituted or unsubstituted benzothieno[3,2-b]carbazol-9-yl group is employ able. Also a substituted or unsubstituted benzothieno[2,3-c]carbazol-9-yl group is employ able. Also a substituted or unsubstituted benzothieno[3,2-c]carbazol-9-yl group is employable.

A preferred benzothiophene-condensed carbazol-9-yl group is a carbazol-9-yl group in which only one benzothiophene ring is condensed at 2,3-positions and any other hetero ring is not condensed (in which, however, a benzene ring can be condensed). Specifically, preferred are groups having any of the following structures, and in the following structures, the hydrogen atom can be substituted. For example, preferably exemplified are those in which a part of the hydrogen atoms in the following structure are substituted with deuterium atoms, or those in which all hydrogen atoms in the following structure are substituted with deuterium atoms. Unsubstituted structures are also preferably employable.

Also preferred is a carbazol-9-yl group in which two benzothiophene rings are condensed at 2,3-positions and any other hetero ring is condensed therein (in which, however, a benzene ring can be condensed). Specifically, preferred are groups having any of the following structures, and in the following structures, the hydrogen atom can be substituted. For example, preferably exemplified are those in which a part of the hydrogen atoms in the following structure are substituted with deuterium atoms, or those in which all hydrogen atoms in the following structure are substituted with deuterium atoms. Unsubstituted structures are also preferably employable.

In the present invention, as the indole-condensed carbazol-9-yl group, a substituted or unsubstituted indolo[2,3-a]carbazol-9-yl group is employable. Also a substituted or unsubstituted indolo[3,2-a]carbazol-9-yl group is employable. Also, a substituted or unsubstituted indolo[2,3-b]carbazol-9-yl group is employable. Also a substituted or unsubstituted indolo[3,2-b]carbazol-9-yl group is employable. Also a substituted or unsubstituted indolo[2,3-c]carbazol-9-yl group is employable. Also a substituted or unsubstituted indolo[3,2-c]carbazol-9-yl group is employable.

A preferred indolo-condensed carbazol-9-yl group is a carbazol-9-yl group in which only one indole ring is condensed at 2,3-positions and any other hetero ring is not condensed (in which, however, a benzene ring can be condensed). Specifically, preferred are groups having any of the following structures, and in the following structures, R′ represents a hydrogen atom, a deuterium atom or a substituent, and preferably, R′ is a substituent. R′ is preferably a substituted or unsubstituted aryl group. In the following structures, the hydrogen atom can be substituted. For example, preferably exemplified are those in which a part of the hydrogen atoms in the following structure are substituted with deuterium atoms, or those in which all hydrogen atoms in the following structure are substituted with deuterium atoms. Unsubstituted structures are also preferably employable.

The hetero ring and the carbazole ring constituting the hetero ring-condensed carbazol-9-yl group each can be substituted. In the case where the rings are substituted, they may be substituted with a deuterium atom or can be substituted with any other substituent. The substituent as referred to herein includes an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, a heteroaryloxy group, a heteroarylthio group, and a cyano group. These substituents can be substituted with any other substituents. For example, there are mentioned embodiments substituted with a deuterium atom, an alkyl group, an aryl group, an alkoxy group or an alkylthio group.

The “alkyl group” as referred to herein may be any of a linear, branched or cyclic one. The group may have two or more kinds of a linear moiety, a cyclic moiety and a branched moiety as combined. The carbon number of the alkyl group may be, for example, 1 or more, 2 or more, or 4 or more. The carbon number may be 30 or less, 20 or less, 10 or less, 6 or less, or 4 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, an isohexyl group, a 2-ethylhexyl group, an n-heptyl group, an isoheptyl group, an n-octyl group, an isooctyl group, an n-nonyl group, an isononyl group, an n-decanyl group, an isodecanyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. The alkyl group to be a substituent may be further substituted with a deuterium atom, an aryl group, an alkoxy group, an aryloxy group or a halogen atom.

The “alkenyl group” as referred to herein may be any of a linear, branched or cyclic one. The group may have two or more kinds of a linear moiety, a cyclic moiety and a branched moiety as combined. The carbon number of the alkenyl group may be, for example, 2 or more, or 4 or more. The carbon number may be 30 or less, 20 or less, 10 or less, 6 or less, or 4 or less. Specific examples of the alkenyl group include an ethenyl group, an n-propenyl group, an isopropenyl group, an n-butenyl group, an isobutenyl group, an n-pentenyl group, an isopentenyl group, an n-hexenyl group, an isohexenyl group, and a 2-ethylhexenyl group. The alkenyl group to be a substituent may be further substituted.

The “aryl group” and the “heteroaryl group” each may be a single ring or may be a condensed ring of two or more kinds of rings. In the case of a condensed ring, the number of the rings that are condensed is preferably 2 to 6, and, for example, can be selected from 2 to 4. Specific examples of the ring include a benzene ring, a pyridine ring, a pyrimidine ring, a triazine ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a triphenylene ring, a quinoline ring, a pyrazine ring, a quinoxaline ring, and a naphthyridine ring. Specific examples of the arylene group or the heteroarylene group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a 2-pyridyl group, a 3-pyridyl group, and a 4-pyridyl group.

Regarding the alkyl moiety in the “alkoxy group” and the “alkylthio group”, reference can be made to the description and the specific examples of the alkyl group mentioned above. Regarding the aryl moiety in the “aryloxy group” and the “arylthio group”, reference can be made to the description and the specific examples of the aryl group mentioned above. Regarding the heteroaryl moiety in the “heteroaryloxy group” and the “heteroarylthio group”, reference can be made to the description and the specific examples of the heteroaryl group mentioned above.

The number of the atoms except hydrogen atoms and deuterium atoms constituting the hetero ring-condensed carbazol-9-yl group is preferably 16 or more, more preferably 20 or more, and can be, for example 16 or more. Also preferably the number is 80 or less, more preferably 50 or less, even more preferably 30 or less.

In the general formula (1), the hetero ring-condensed carbazol-9-yl group can be D¹ alone, or can be D² alone. In one preferred embodiment of the present invention, D¹ and D² are both hetero ring-condensed carbazol-9-yl groups. In that case, D¹ and D² can have the same structure, or can be different hetero ring-condensed carbazol-9-yl groups.

In the case where any one of D¹ and D² is a hetero ring-condensed carbazol-9-yl group, the other is a donor group except the hetero ring-condensed carbazol-9-yl (hereinafter this is referred to as “the other donor group”). The other donor group as referred to herein is a group having a negative Hammett's op value. Here, “Hammett's σ_(p) value” is one propounded by L. P. Hammett, and is one to quantify the influence of a substituent on the reaction rate or the equilibrium of a para-substituted benzene derivative. Specifically, the value is a constant (σ_(p)) peculiar to the substituent in the following equation that is established between a substituent and a reaction rate constant or an equilibrium constant in a para-substituted benzene derivative:

log(k/k ₀)=ρσ_(p)

or

log(K/K ₀)=ρσ_(p)

In the above equations, k represents a rate constant of a benzene derivative not having a substituent; k₀ represents a rate constant of a benzene derivative substituted with a substituent; K represents an equilibrium constant of a benzene derivative not having a substituent; K₀ represents an equilibrium constant of a benzene derivative substituted with a substituent; ρ represents a reaction constant to be determined by the kind and the condition of reaction. Regarding the description relating to the “Hammett's σ_(p) value” and the numerical value of each substituent in the present invention, reference may be made to the description relating to σ_(p) value in Hansch. C. et. al., Chem. Rev., 91, 165-195 (1991). A group having a negative Hammett's σ_(p) value tends to exhibit an electron donor property, and a group having a positive Hammett's σ_(p) value tends to exhibit an electron acceptor property.

The other donor group in the present invention is preferably a group containing a substituted amino group. The substituent bonding to the nitrogen atom of the amino group is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, more preferably a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. Especially, the substituted amino group is preferably a substituted or unsubstituted diarylamino group or a substituted or unsubstituted diheteroarylamino group. In the present invention, the donor group can be a group bonding at the nitrogen atom of a substituted amino group, or can be a group bonding to the substituted amino group-bonding group. The substituted amino group-bonding group is preferably a n-conjugated group. More preferred is a group bonding at the nitrogen atom of the substituted amino group. Regarding the alkyl group, the alkenyl group, the aryl group and the heteroaryl group as referred to herein as substituents, reference can be made to the corresponding description relating to the substituents for the aromatic hydrocarbon ring group and the aromatic hetero ring group mentioned hereinabove.

The other donor group especially preferred in the present invention is a substituted or unsubstituted carbazol-9-yl group. The carbazol-9-yl group can be condensed with a benzene ring or a hetero ring (excepting a benzofuran ring, a benzothiophene ring, an indole ring, an indene ring and a silaindene ring). The substituent for the carbazol-9-yl group includes an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, a heteroaryloxy group, a heteroarylthio group, and a substituted amino group. Preferred substituents are an alkyl group, an aryl group and a substituted amino group. Regarding the description of the substituted amin group, reference can be made to the description in the preceding paragraph. The substituted amino group as referred to herein includes a substituted or unsubstituted carbazolyl group, and for example, includes a substituted or unsubstituted carbazol-3-yl group and a substituted or unsubstituted carbazol-9-yl group.

The number of the atoms except hydrogen atoms and deuterium atoms constituting the other donor group in the present invention is preferably 8 or more, more preferably 12 or more, and for example, can be 16 or more. Also preferably the number is 80 or less, more preferably 60 or less, even more preferably 40 or less.

In the following, specific examples of the donor group that D¹ and D² in the general formula (1) can represent are shown. D13 to D78, D84 to D119, D150 to D161, D168 to D209, D215 to D268, and D270 to D324 are specific examples of a hetero ring-condensed carbazol-9-1 group, and D1 to D12, D79 to 83, D120 to 149, D162 to D167, D210 to D214, and D269 are specific examples of other donor groups. In the following structural formulae. Ph represents a phenyl group, and * indicates a bonding position.

R in the general formula (1) represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group bonding via a carbon atom. In one preferred embodiment of the present invention, R is a hydrogen atom or a deuterium atom. However, herein also employable are an embodiment where R is a substituted or unsubstituted aryl group, and an embodiment where R is a substituted or unsubstituted heteroaryl group bonding via a carbon atom. In the case where R is an aryl group, it is preferably a substituted aryl group. In the case where R is a heteroaryl group, it is preferably a substituted heteroaryl group.

Ar in the general formula (1) represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group bonding via a carbon atom. In one preferred embodiment of the present invention, Ar is a substituted or unsubstituted aryl group. However, herein also employable is an embodiment where Ar is a substituted or unsubstituted heteroaryl group

Regarding the description and the preferred range of the aryl group and the heteroaryl group that R and Ar can represent, reference can be made to the description of the aryl group and the heteroaryl group in the substituent for the hetero ring-condensed carbazol-9-yl group. However, the heteroaryl group is a heteroaryl group bonding via a carbon atoms. The substituent for the aryl group and the substituent for the heteroaryl group include an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, a heteroaryloxy group, a heteroarylthio group and a cyano group. These substituents can be further substituted with any other substituent. The group of preferred substituents includes an alkyl group, an aryl group, an alkoxy group, an alkylthio group and a cyano group.

In one preferred embodiment of the present invention, R is a hydrogen atom or a deuterium atom, and Ar is a substituted or unsubstituted phenyl group, in which the phenyl group can be condensed with one or more rings selected from a benzene ring, a pyridine ring, a furan ring, a thiophene ring and a pyrrole ring. In another preferred embodiment of the present invention. R is a hydrogen atom or a deuterium atom, and Ar is a substituted or unsubstituted pyridyl group, in which the pyridyl group can be condensed with one or more rings selected from a benzene ring, a pyridine ring, a furan ring, a thiophene ring and a pyrrole ring. In another preferred embodiment of the present invention, R is a hydrogen atom or a deuterium atom, and Ar is a substituted phenyl group, in which the phenyl group is substituted with one or more groups selected from a substituted or unsubstituted phenyl group, and a substituted or unsubstituted pyridyl group. In another preferred embodiment of the present invention, R is a hydrogen atom or a deuterium atom, and Ar is a substituted pyridyl group, in which the pyridyl group is substituted with one or more groups selected from a substituted or unsubstituted phenyl group, and a substituted or unsubstituted pyridyl group.

In the following, shown are specific examples of the substituted or unsubstituted aryl group which can be employed by R and Ar in the general formula (1), and the substituted or unsubstituted heteroaryl group bonding via a carbon atom. In the following structural formulae, * indicates a bonding position.

The compound represented by the general formula (1) can be a compound composed of atoms alone selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, an oxygen atom and a sulfur atom. In one preferred embodiment of the present invention, the compound represented by the general formula (1) is composed of atoms alone selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, and an oxygen atom. The compound represented by the general formula (1) can also be a compound composed of atoms alone selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom and a sulfur atom. The compound represented by the general formula (1) can also be a compound composed of atoms alone selected from the group consisting of a carbon atom, a hydrogen atom and a nitrogen atom. Further, the compound represented by the general formula (1) can be a compound not containing a hydrogen atom but containing a deuterium atom. For example, the compound represented by the general formula (1) can be a compound composed of atoms alone selected from the group consisting of a carbon atom, a deuterium atom, a nitrogen atom, an oxygen atom and a sulfur atom.

In one embodiment of the present invention, the compound represented by the general formula (1) has a symmetric structure.

In one preferred embodiment of the present invention, the compound represented by the general formula (1) has a structure represented by the following general formula (2).

In one preferred embodiment of the present invention, the compound represented by the general formula (1) has a structure represented by the following general formula (3).

Regarding the definition and the description of R, Ar, D¹ and D² in the general formula (2) and the general formula (3), reference can be made to the corresponding description of the general formula (1).

In the following, shown are specific examples of the compound represented by the general formula (1). Specific examples show individual compounds by defining R¹ to R⁴ in the following general formula. R in the general formula (1) corresponds to R¹ in the following general formula, and D¹ in the general formula corresponds to R² in the following general formula. In the case where the following compounds have rotational isomers, a mixture of the rotational isomers and each isolated rotational isomer are considered to be disclosed in the present description.

TABLE 1 R¹ = H No. R² R³ R⁴ 1 D15 D15 Ar1 2 D16 3 D18 4 D21 5 D33 6 D34 7 D36 8 D45 9 D46 10 D48 11 D63 12 D64 13 D66 14 D73 15 D74 16 D75 17 D76 18 D78 19 D155 20 D182 21 D183 22 D185 23 D246 24 D265 25 D266 26 D267 27 D268 28 D269 29 D296 30 D298 31 D15 D16 32 D16 33 D18 34 D21 35 D33 36 D34 37 D36 38 D45 39 D46 40 D48 41 D63 42 D64 43 D66 44 D73 45 D74 46 D75 47 D76 48 D78 49 D155 50 D182 51 D183 52 D185 53 D246 54 D265 55 D266 56 D267 57 D268 58 D269 59 D296 60 D298 61 D15 D18 Ar1 62 D16 63 D18 64 D21 65 D33 66 D34 67 D36 68 D45 69 D46 70 D48 71 D63 72 D64 73 D66 74 D73 75 D74 76 D75 77 D76 78 D78 79 D155 80 D182 81 D183 82 D185 83 D246 84 D265 85 D266 86 D267 87 D268 88 D269 89 D296 90 D298 91 D15 D21 92 D16 93 D18 94 D21 95 D33 96 D34 97 D36 98 D45 99 D46 100 D48 101 D63 102 D64 103 D66 104 D73 105 D74 106 D75 107 D76 108 D78 109 D155 110 D182 111 D183 112 D185 113 D246 114 D265 115 D266 116 D267 117 D268 118 D269 119 D296 120 D298 121 D15 D33 Ar1 122 D16 123 D18 124 D21 125 D33 126 D34 127 D36 128 D45 129 D46 130 D48 131 D63 132 D64 133 D66 134 D73 135 D74 136 D75 137 D76 138 D78 139 D155 140 D182 141 D183 142 D185 143 D246 144 D265 145 D266 146 D267 147 D268 148 D269 149 D296 150 D298 151 D15 D34 152 D16 153 D18 154 D21 155 D33 156 D34 157 D36 158 D45 159 D46 160 D48 161 D63 162 D64 163 D66 164 D73 165 D74 166 D75 167 D76 168 D78 169 D155 170 D182 171 D183 172 D185 173 D246 174 D265 175 D266 176 D267 177 D268 178 D269 179 D296 180 D298 181 D15 D36 Ar1 182 D16 183 D18 184 D21 185 D33 186 D34 187 D36 188 D45 189 D46 190 D48 191 D63 192 D64 193 D66 194 D73 195 D74 196 D75 197 D76 198 D78 199 D155 200 D182 201 D183 202 D185 203 D246 204 D265 205 D266 206 D267 207 D268 208 D269 209 D296 210 D298 211 D15 D45 212 D16 213 D18 214 D21 215 D33 216 D34 217 D36 218 D45 219 D46 220 D48 221 D63 222 D64 223 D66 224 D73 225 D74 226 D75 227 D76 228 D78 229 D155 230 D182 231 D183 232 D185 233 D246 234 D265 235 D266 236 D267 237 D268 238 D269 239 D296 240 D298 241 D15 D46 Ar1 242 D16 243 D18 244 D21 245 D33 246 D34 247 D36 248 D45 249 D46 250 D48 251 D63 252 D64 253 D66 254 D73 255 D74 256 D75 257 D76 258 D78 259 D155 260 D182 261 D183 262 D185 263 D246 264 D265 265 D266 266 D267 267 D268 268 D269 269 D296 270 D298 271 D15 D48 272 D16 273 D18 274 D21 275 D33 276 D34 277 D36 278 D45 279 D46 280 D48 281 D63 282 D64 283 D66 284 D73 285 D74 286 D75 287 D76 288 D78 289 D155 290 D182 291 D183 292 D185 293 D246 294 D265 295 D266 296 D267 297 D268 298 D269 299 D296 300 D298 301 D15 D63 Ar1 302 D16 303 D18 304 D21 305 D33 306 D34 307 D36 308 D45 309 D46 310 D48 311 D63 312 D64 313 D66 314 D73 315 D74 316 D75 317 D76 318 D78 319 D155 320 D182 321 D183 322 D185 323 D246 324 D265 325 D266 326 D267 327 D268 328 D269 329 D296 330 D298 331 D15 D64 332 D16 333 D18 334 D21 335 D33 336 D34 337 D36 338 D45 339 D46 340 D48 341 D63 342 D64 343 D66 344 D73 345 D74 346 D75 347 D76 348 D78 349 D155 350 D182 351 D183 352 D185 353 D246 354 D265 355 D266 356 D267 357 D268 358 D269 359 D296 360 D298 361 D15 D66 Ar1 362 D16 363 D18 364 D21 365 D33 366 D34 367 D36 368 D45 369 D46 370 D48 371 D63 372 D64 373 D66 374 D73 375 D74 376 D75 377 D76 378 D78 379 D155 380 D182 381 D183 382 D185 383 D246 384 D265 385 D266 386 D267 387 D268 388 D269 389 D296 390 D298 391 D15 D73 392 D16 393 D18 394 D21 395 D33 396 D34 397 D36 398 D45 399 D46 400 D48 401 D63 402 D64 403 D66 404 D73 405 D74 406 D75 407 D76 408 D78 409 D155 410 D182 411 D183 412 D185 413 D246 414 D265 415 D266 416 D267 417 D268 418 D269 419 D296 420 D298 421 D15 D74 Ar1 422 D16 423 D18 424 D21 425 D33 426 D34 427 D36 428 D45 429 D46 430 D48 431 D63 432 D64 433 D66 434 D73 435 D74 436 D75 437 D76 438 D78 439 D155 440 D182 441 D183 442 D185 443 D246 444 D265 445 D266 446 D267 447 D268 448 D269 449 D296 450 D298 451 D15 D75 452 D16 453 D18 454 D21 455 D33 456 D34 457 D36 458 D45 459 D46 460 D48 461 D63 462 D64 463 D66 464 D73 465 D74 466 D75 467 D76 468 D78 469 D155 470 D182 471 D183 472 D185 473 D246 474 D265 475 D266 476 D267 477 D268 478 D269 479 D296 480 D298 481 D15 D76 Ar1 482 D16 483 D18 484 D21 485 D33 486 D34 487 D36 488 D45 489 D46 490 D48 491 D63 492 D64 493 D66 494 D73 495 D74 496 D75 497 D76 498 D78 499 D155 500 D182 501 D183 502 D185 503 D246 504 D265 505 D266 506 D267 507 D268 508 D269 509 D296 510 D298 511 D15 D78 512 D16 513 D18 514 D21 515 D33 516 D34 517 D36 518 D45 519 D46 520 D48 521 D63 522 D64 523 D66 524 D73 525 D74 526 D75 527 D76 528 D78 529 D155 530 D182 531 D183 532 D185 533 D246 534 D265 535 D266 536 D267 537 D268 538 D269 539 D296 540 D298 541 D15 D155 Ar1 542 D16 543 D18 544 D21 545 D33 546 D34 547 D36 548 D45 549 D46 550 D48 551 D63 552 D64 553 D66 554 D73 555 D74 556 D75 557 D76 558 D78 559 D155 560 D182 561 D183 562 D185 563 D246 564 D265 565 D266 566 D267 567 D268 568 D269 569 D296 570 D298 571 D15 D182 572 D16 573 D18 574 D21 575 D33 576 D34 577 D36 578 D45 579 D46 580 D48 581 D63 582 D64 583 D66 584 D73 585 D74 586 D75 587 D76 588 D78 589 D155 590 D182 591 D183 592 D185 593 D246 594 D265 595 D266 596 D267 597 D268 598 D269 599 D296 600 D298 601 D15 D183 Ar1 602 D16 603 D18 604 D21 605 D33 606 D34 607 D36 608 D45 609 D46 610 D48 611 D63 612 D64 613 D66 614 D73 615 D74 616 D75 617 D76 618 D78 619 D155 620 D182 621 D183 622 D185 623 D246 624 D265 625 D266 626 D267 627 D268 628 D269 629 D296 630 D298 631 D15 D185 632 D16 633 D18 634 D21 635 D33 636 D34 637 D36 638 D45 639 D46 640 D48 641 D63 642 D64 643 D66 644 D73 645 D74 646 D75 647 D76 648 D78 649 D155 650 D182 651 D183 652 D185 653 D246 654 D265 655 D266 656 D267 657 D268 658 D269 659 D296 660 D298 661 D15 D246 Ar1 662 D16 663 D18 664 D21 665 D33 666 D34 667 D36 668 D45 669 D46 670 D48 671 D63 672 D64 673 D66 674 D73 675 D74 676 D75 677 D76 678 D78 679 D155 680 D182 681 D183 682 D185 683 D246 684 D265 685 D266 686 D267 687 D268 688 D269 689 D296 690 D298 691 D15 D265 692 D16 693 D18 694 D21 695 D33 696 D34 697 D36 698 D45 699 D46 700 D48 701 D63 702 D64 703 D66 704 D73 705 D74 706 D75 707 D76 708 D78 709 D155 710 D182 711 D183 712 D185 713 D246 714 D265 715 D266 716 D267 717 D268 718 D269 719 D296 720 D298 721 D15 D266 Ar1 722 D16 723 D18 724 D21 725 D33 726 D34 727 D36 728 D45 729 D46 730 D48 731 D63 732 D64 733 D66 734 D73 735 D74 736 D75 737 D76 738 D78 739 D155 740 D182 741 D183 742 D185 743 D246 744 D265 745 D266 746 D267 747 D268 748 D269 749 D296 750 D298 751 D15 D267 752 D16 753 D18 754 D21 755 D33 756 D34 757 D36 758 D45 759 D46 760 D48 761 D63 762 D64 763 D66 764 D73 765 D74 766 D75 767 D76 768 D78 769 D155 770 D182 771 D183 772 D185 773 D246 774 D265 775 D266 776 D267 777 D268 778 D269 779 D296 780 D298 781 D15 D268 Ar1 782 D16 783 D18 784 D21 785 D33 786 D34 787 D36 788 D45 789 D46 790 D48 791 D63 792 D64 793 D66 794 D73 795 D74 796 D75 797 D76 798 D78 799 D155 800 D182 801 D183 802 D185 803 D246 804 D265 805 D266 806 D267 807 D268 808 D269 809 D296 810 D298 811 D15 D269 812 D16 813 D18 814 D21 815 D33 816 D34 817 D36 818 D45 819 D46 820 D48 821 D63 822 D64 823 D66 824 D73 825 D74 826 D75 827 D76 828 D78 829 D155 830 D182 831 D183 832 D185 833 D246 834 D265 835 D266 836 D267 837 D268 838 D269 839 D296 840 D298 841 D15 D296 Ar1 842 D16 843 D18 844 D21 845 D33 846 D34 847 D36 848 D45 849 D46 850 D48 851 D63 852 D64 853 D66 854 D73 855 D74 856 D75 857 D76 858 D78 859 D155 860 D182 861 D183 862 D185 863 D246 864 D265 865 D266 866 D267 867 D268 868 D269 869 D296 870 D298 871 D15 D298 872 D16 873 D18 874 D21 875 D33 876 D34 877 D36 878 D45 879 D46 880 D48 881 D63 882 D64 883 D66 884 D73 885 D74 886 D75 887 D76 888 D78 889 D155 890 D182 891 D183 892 D185 893 D246 894 D265 895 D266 896 D267 897 D268 898 D269 899 D296 900 D298 901 D15 D15 Ar16 902 D16 903 D18 904 D21 905 D33 906 D34 907 D36 908 D45 909 D46 910 D48 911 D63 912 D64 913 D66 914 D73 915 D74 916 D75 917 D76 918 D78 919 D155 920 D182 921 D183 922 D185 923 D246 924 D265 925 D266 926 D267 927 D268 928 D269 929 D296 930 D298 931 D15 D16 932 D16 933 D18 934 D21 935 D33 936 D34 937 D36 938 D45 939 D46 940 D48 941 D63 942 D64 943 D66 944 D73 945 D74 946 D75 947 D76 948 D78 949 D155 950 D182 951 D183 952 D185 953 D246 954 D265 955 D266 956 D267 957 D268 958 D269 959 D296 960 D298 961 D15 D18 Ar16 962 D16 963 D18 964 D21 965 D33 966 D34 967 D36 968 D45 969 D46 970 D48 971 D63 972 D64 973 D66 974 D73 975 D74 976 D75 977 D76 978 D78 979 D155 980 D182 981 D183 982 D185 983 D246 984 D265 985 D266 986 D267 987 D268 988 D269 989 D296 990 D298 991 D15 D21 992 D16 993 D18 994 D21 995 D33 996 D34 997 D36 998 D45 999 D46 1000 D48 1001 D63 1002 D64 1003 D66 1004 D73 1005 D74 1006 D75 1007 D76 1008 D78 1009 D155 1010 D182 1011 D183 1012 D185 1013 D246 1014 D265 1015 D266 1016 D267 1017 D268 1018 D269 1019 D296 1020 D298 1021 D15 D33 Ar16 1022 D16 1023 D18 1024 D21 1025 D33 1026 D34 1027 D36 1028 D45 1029 D46 1030 D48 1031 D63 1032 D64 1033 D66 1034 D73 1035 D74 1036 D75 1037 D76 1038 D78 1039 D155 1040 D182 1041 D183 1042 D185 1043 D246 1044 D265 1045 D266 1046 D267 1047 D268 1048 D269 1049 D296 1050 D298 1051 D15 D34 1052 D16 1053 D18 1054 D21 1055 D33 1056 D34 1057 D36 1058 D45 1059 D46 1060 D48 1061 D63 1062 D64 1063 D66 1064 D73 1065 D74 1066 D75 1067 D76 1068 D78 1069 D155 1070 D182 1071 D183 1072 D185 1073 D246 1074 D265 1075 D266 1076 D267 1077 D268 1078 D269 1079 D296 1080 D298 1081 D15 D36 Ar16 1082 D16 1083 D18 1084 D21 1085 D33 1086 D34 1087 D36 1088 D45 1089 D46 1090 D48 1091 D63 1092 D64 1093 D66 1094 D73 1095 D74 1096 D75 1097 D76 1098 D78 1099 D155 1100 D182 1101 D183 1102 D185 1103 D246 1104 D265 1105 D266 1106 D267 1107 D268 1108 D269 1109 D296 1110 D298 1111 D15 D45 1112 D16 1113 D18 1114 D21 1115 D33 1116 D34 1117 D36 1118 D45 1119 D46 1120 D48 1121 D63 1122 D64 1123 D66 1124 D73 1125 D74 1126 D75 1127 D76 1128 D78 1129 D155 1130 D182 1131 D183 1132 D185 1133 D246 1134 D265 1135 D266 1136 D267 1137 D268 1138 D269 1139 D296 1140 D298 1141 D15 D46 Ar16 1142 D16 1143 D18 1144 D21 1145 D33 1146 D34 1147 D36 1148 D45 1149 D46 1150 D48 1151 D63 1152 D64 1153 D66 1154 D73 1155 D74 1156 D75 1157 D76 1158 D78 1159 D155 1160 D182 1161 D183 1162 D185 1163 D246 1164 D265 1165 D266 1166 D267 1167 D268 1168 D269 1169 D296 1170 D298 1171 D15 D48 1172 D16 1173 D18 1174 D21 1175 D33 1176 D34 1177 D36 1178 D45 1179 D46 1180 D48 1181 D63 1182 D64 1183 D66 1184 D73 1185 D74 1186 D75 1187 D76 1188 D78 1189 D155 1190 D182 1191 D183 1192 D185 1193 D246 1194 D265 1195 D266 1196 D267 1197 D268 1198 D269 1199 D296 1200 D298 1201 D15 D63 Ar16 1202 D16 1203 D18 1204 D21 1205 D33 1206 D34 1207 D36 1208 D45 1209 D46 1210 D48 1211 D63 1212 D64 1213 D66 1214 D73 1215 D74 1216 D75 1217 D76 1218 D78 1219 D155 1220 D182 1221 D183 1222 D185 1223 D246 1224 D265 1225 D266 1226 D267 1227 D268 1228 D269 1229 D296 1230 D298 1231 D15 D64 1232 D16 1233 D18 1234 D21 1235 D33 1236 D34 1237 D36 1238 D45 1239 D46 1240 D48 1241 D63 1242 D64 1243 D66 1244 D73 1245 D74 1246 D75 1247 D76 1248 D78 1249 D155 1250 D182 1251 D183 1252 D185 1253 D246 1254 D265 1255 D266 1256 D267 1257 D268 1258 D269 1259 D296 1260 D298 1261 D15 D66 Ar16 1262 D16 1263 D18 1264 D21 1265 D33 1266 D34 1267 D36 1268 D45 1269 D46 1270 D48 1271 D63 1272 D64 1273 D66 1274 D73 1275 D74 1276 D75 1277 D76 1278 D78 1279 D155 1280 D182 1281 D183 1282 D185 1283 D246 1284 D265 1285 D266 1286 D267 1287 D268 1288 D269 1289 D296 1290 D298 1291 D15 D73 1292 D16 1293 D18 1294 D21 1295 D33 1296 D34 1297 D36 1298 D45 1299 D46 1300 D48 1301 D63 1302 D64 1303 D66 1304 D73 1305 D74 1306 D75 1307 D76 1308 D78 1309 D155 1310 D182 1311 D183 1312 D185 1313 D246 1314 D265 1315 D266 1316 D267 1317 D268 1318 D269 1319 D296 1320 D298 1321 D15 D74 Ar16 1322 D16 1323 D18 1324 D21 1325 D33 1326 D34 1327 D36 1328 D45 1329 D46 1330 D48 1331 D63 1332 D64 1333 D66 1334 D73 1335 D74 1336 D75 1337 D76 1338 D78 1339 D155 1340 D182 1341 D183 1342 D185 1343 D246 1344 D265 1345 D266 1346 D267 1347 D268 1348 D269 1349 D296 1350 D298 1351 D15 D75 1352 D16 1353 D18 1354 D21 1355 D33 1356 D34 1357 D36 1358 D45 1359 D46 1360 D48 1361 D63 1362 D64 1363 D66 1364 D73 1365 D74 1366 D75 1367 D76 1368 D78 1369 D155 1370 D182 1371 D183 1372 D185 1373 D246 1374 D265 1375 D266 1376 D267 1377 D268 1378 D269 1379 D296 1380 D298 1381 D15 D76 Ar16 1382 D16 1383 D18 1384 D21 1385 D33 1386 D34 1387 D36 1388 D45 1389 D46 1390 D48 1391 D63 1392 D64 1393 D66 1394 D73 1395 D74 1396 D75 1397 D76 1398 D78 1399 D155 1400 D182 1401 D183 1402 D185 1403 D246 1404 D265 1405 D266 1406 D267 1407 D268 1408 D269 1409 D296 1410 D298 1411 D15 D78 1412 D16 1413 D18 1414 D21 1415 D33 1416 D34 1417 D36 1418 D45 1419 D46 1420 D48 1421 D63 1422 D64 1423 D66 1424 D73 1425 D74 1426 D75 1427 D76 1428 D78 1429 D155 1430 D182 1431 D183 1432 D185 1433 D246 1434 D265 1435 D266 1436 D267 1437 D268 1438 D269 1439 D296 1440 D298 1441 D15 D155 Ar16 1442 D16 1443 D18 1444 D21 1445 D33 1446 D34 1447 D36 1448 D45 1449 D46 1450 D48 1451 D63 1452 D64 1453 D66 1454 D73 1455 D74 1456 D75 1457 D76 1458 D78 1459 D155 1460 D182 1461 D183 1462 D185 1463 D246 1464 D265 1465 D266 1466 D267 1467 D268 1468 D269 1469 D296 1470 D298 1471 D15 D182 1472 D16 1473 D18 1474 D21 1475 D33 1476 D34 1477 D36 1478 D45 1479 D46 1480 D48 1481 D63 1482 D64 1483 D66 1484 D73 1485 D74 1486 D75 1487 D76 1488 D78 1489 D155 1490 D182 1491 D183 1492 D185 1493 D246 1494 D265 1495 D266 1496 D267 1497 D268 1498 D269 1499 D296 1500 D298 1501 D15 D183 Ar16 1502 D16 1503 D18 1504 D21 1505 D33 1506 D34 1507 D36 1508 D45 1509 D46 1510 D48 1511 D63 1512 D64 1513 D66 1514 D73 1515 D74 1516 D75 1517 D76 1518 D78 1519 D155 1520 D182 1521 D183 1522 D185 1523 D246 1524 D265 1525 D266 1526 D267 1527 D268 1528 D269 1529 D296 1530 D298 1531 D15 D185 1532 D16 1533 D18 1534 D21 1535 D33 1536 D34 1537 D36 1538 D45 1539 D46 1540 D48 1541 D63 1542 D64 1543 D66 1544 D73 1545 D74 1546 D75 1547 D76 1548 D78 1549 D155 1550 D182 1551 D183 1552 D185 1553 D246 1554 D265 1555 D266 1556 D267 1557 D268 1558 D269 1559 D296 1560 D298 1561 D15 D246 Ar16 1562 D16 1563 D18 1564 D21 1565 D33 1566 D34 1567 D36 1568 D45 1569 D46 1570 D48 1571 D63 1572 D64 1573 D66 1574 D73 1575 D74 1576 D75 1577 D76 1578 D78 1579 D155 1580 D182 1581 D183 1582 D185 1583 D246 1584 D265 1585 D266 1586 D267 1587 D268 1588 D269 1589 D296 1590 D298 1591 D15 D265 1592 D16 1593 D18 1594 D21 1595 D33 1596 D34 1597 D36 1598 D45 1599 D46 1600 D48 1601 D63 1602 D64 1603 D66 1604 D73 1605 D74 1606 D75 1607 D76 1608 D78 1609 D155 1610 D182 1611 D183 1612 D185 1613 D246 1614 D265 1615 D266 1616 D267 1617 D268 1618 D269 1619 D296 1620 D298 1621 D15 D266 Ar16 1622 D16 1623 D18 1624 D21 1625 D33 1626 D34 1627 D36 1628 D45 1629 D46 1630 D48 1631 D63 1632 D64 1633 D66 1634 D73 1635 D74 1636 D75 1637 D76 1638 D78 1639 D155 1640 D182 1641 D183 1642 D185 1643 D246 1644 D265 1645 D266 1646 D267 1647 D268 1648 D269 1649 D296 1650 D298 1651 D15 D267 1652 D16 1653 D18 1654 D21 1655 D33 1656 D34 1657 D36 1658 D45 1659 D46 1660 D48 1661 D63 1662 D64 1663 D66 1664 D73 1665 D74 1666 D75 1667 D76 1668 D78 1669 D155 1670 D182 1671 D183 1672 D185 1673 D246 1674 D265 1675 D266 1676 D267 1677 D268 1678 D269 1679 D296 1680 D298 1681 D15 D268 Ar16 1682 D16 1683 D18 1684 D21 1685 D33 1686 D34 1687 D36 1688 D45 1689 D46 1690 D48 1691 D63 1692 D64 1693 D66 1694 D73 1695 D74 1696 D75 1697 D76 1698 D78 1699 D155 1700 D182 1701 D183 1702 D185 1703 D246 1704 D265 1705 D266 1706 D267 1707 D268 1708 D269 1709 D296 1710 D298 1711 D15 D269 1712 D16 1713 D18 1714 D21 1715 D33 1716 D34 1717 D36 1718 D45 1719 D46 1720 D48 1721 D63 1722 D64 1723 D66 1724 D73 1725 D74 1726 D75 1727 D76 1728 D78 1729 D155 1730 D182 1731 D183 1732 D185 1733 D246 1734 D265 1735 D266 1736 D267 1737 D268 1738 D269 1739 D296 1740 D298 1741 D15 D296 Ar16 1742 D16 1743 D18 1744 D21 1745 D33 1746 D34 1747 D36 1748 D45 1749 D46 1750 D48 1751 D63 1752 D64 1753 D66 1754 D73 1755 D74 1756 D75 1757 D76 1758 D78 1759 D155 1760 D182 1761 D183 1762 D185 1763 D246 1764 D265 1765 D266 1766 D267 1767 D268 1768 D269 1769 D296 1770 D298 1771 D15 D298 1772 D16 1773 D18 1774 D21 1775 D33 1776 D34 1777 D36 1778 D45 1779 D46 1780 D48 1781 D63 1782 D64 1783 D66 1784 D73 1785 D74 1786 D75 1787 D76 1788 D78 1789 D155 1790 D182 1791 D183 1792 D185 1793 D246 1794 D265 1795 D266 1796 D267 1797 D268 1798 D269 1799 D296 1800 D298 1801 D15 D15 Ar21 1802 D16 1803 D18 1804 D21 1805 D33 1806 D34 1807 D36 1808 D45 1809 D46 1810 D48 1811 D63 1812 D64 1813 D66 1814 D73 1815 D74 1816 D75 1817 D76 1818 D78 1819 D155 1820 D182 1821 D183 1822 D185 1823 D246 1824 D265 1825 D266 1826 D267 1827 D268 1828 D269 1829 D296 1830 D298 1831 D15 D16 1832 D16 1833 D18 1834 D21 1835 D33 1836 D34 1837 D36 1838 D45 1839 D46 1840 D48 1841 D63 1842 D64 1843 D66 1844 D73 1845 D74 1846 D75 1847 D76 1848 D78 1849 D155 1850 D182 1851 D183 1852 D185 1853 D246 1854 D265 1855 D266 1856 D267 1857 D268 1858 D269 1859 D296 1860 D298 1861 D15 D18 Ar21 1862 D16 1863 D18 1864 D21 1865 D33 1866 D34 1867 D36 1868 D45 1869 D46 1870 D48 1871 D63 1872 D64 1873 D66 1874 D73 1875 D74 1876 D75 1877 D76 1878 D78 1879 D155 1880 D182 1881 D183 1882 D185 1883 D246 1884 D265 1885 D266 1886 D267 1887 D268 1888 D269 1889 D296 1890 D298 1891 D15 D21 1892 D16 1893 D18 1894 D21 1895 D33 1896 D34 1897 D36 1898 D45 1899 D46 1900 D48 1901 D63 1902 D64 1903 D66 1904 D73 1905 D74 1906 D75 1907 D76 1908 D78 1909 D155 1910 D182 1911 D183 1912 D185 1913 D246 1914 D265 1915 D266 1916 D267 1917 D268 1918 D269 1919 D296 1920 D298 1921 D15 D33 Ar21 1922 D16 1923 D18 1924 D21 1925 D33 1926 D34 1927 D36 1928 D45 1929 D46 1930 D48 1931 D63 1932 D64 1933 D66 1934 D73 1935 D74 1936 D75 1937 D76 1938 D78 1939 D155 1940 D182 1941 D183 1942 D185 1943 D246 1944 D265 1945 D266 1946 D267 1947 D268 1948 D269 1949 D296 1950 D298 1951 D15 D34 1952 D16 1953 D18 1954 D21 1955 D33 1956 D34 1957 D36 1958 D45 1959 D46 1960 D48 1961 D63 1962 D64 1963 D66 1964 D73 1965 D74 1966 D75 1967 D76 1968 D78 1969 D155 1970 D182 1971 D183 1972 D185 1973 D246 1974 D265 1975 D266 1976 D267 1977 D268 1978 D269 1979 D296 1980 D298 1981 D15 D36 Ar21 1982 D16 1983 D18 1984 D21 1985 D33 1986 D34 1987 D36 1988 D45 1989 D46 1990 D48 1991 D63 1992 D64 1993 D66 1994 D73 1995 D74 1996 D75 1997 D76 1998 D78 1999 D155 2000 D182 2001 D183 2002 D185 2003 D246 2004 D265 2005 D266 2006 D267 2007 D268 2008 D269 2009 D296 2010 D298 2011 D15 D45 2012 D16 2013 D18 2014 D21 2015 D33 2016 D34 2017 D36 2018 D45 2019 D46 2020 D48 2021 D63 2022 D64 2023 D66 2024 D73 2025 D74 2026 D75 2027 D76 2028 D78 2029 D155 2030 D182 2031 D183 2032 D185 2033 D246 2034 D265 2035 D266 2036 D267 2037 D268 2038 D269 2039 D296 2040 D298 2041 D15 D46 Ar21 2042 D16 2043 D18 2044 D21 2045 D33 2046 D34 2047 D36 2048 D45 2049 D46 2050 D48 2051 D63 2052 D64 2053 D66 2054 D73 2055 D74 2056 D75 2057 D76 2058 D78 2059 D155 2060 D182 2061 D183 2062 D185 2063 D246 2064 D265 2065 D266 2066 D267 2067 D268 2068 D269 2069 D296 2070 D298 2071 D15 D48 2072 D16 2073 D18 2074 D21 2075 D33 2076 D34 2077 D36 2078 D45 2079 D46 2080 D48 2081 D63 2082 D64 2083 D66 2084 D73 2085 D74 2086 D75 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D34 5347 D36 5348 D45 5349 D46 5350 D48 5351 D63 5352 D64 5353 D66 5354 D73 5355 D74 5356 D75 5357 D76 5358 D78 5359 D155 5360 D182 5361 D183 5362 D185 5363 D246 5364 D265 5365 D266 5366 D267 5367 D268 5368 D269 5363 D296 5370 D298 5371 D15 D298 5372 D16 5373 D18 5374 D21 5375 D33 5376 D34 5377 D36 5378 D45 5379 D46 5380 D48 5381 D63 5382 D64 5383 D66 5384 D73 5385 D74 5386 D75 5387 D76 5388 D78 5389 D155 5390 D182 5391 D183 5392 D185 5393 D246 5394 D265 5395 D266 5396 D267 5397 D268 5398 D269 5399 D296 5400 D298 5401 D15 D15 Ar88 5402 D16 5403 D18 5404 D21 5405 D33 5406 D34 5407 D36 5408 D45 5409 D46 5410 D48 5411 D63 5412 D64 5413 D66 5414 D73 5415 D74 5416 D75 5417 D76 5418 D78 5419 D155 5420 D182 5421 D183 5422 D185 5423 D246 5424 D265 5425 D266 5426 D267 5427 D268 5428 D269 5429 D296 5430 D298 5431 D15 D16 5432 D16 5433 D18 5434 D21 5435 D33 5436 D34 5437 D36 5438 D45 5439 D46 5440 D48 5441 D63 5442 D64 5443 D66 5444 D73 5445 D74 5446 D75 5447 D76 5448 D78 5449 D155 5450 D182 5451 D183 5452 D185 5453 D246 5454 D265 5455 D266 5456 D267 5457 D268 5458 D269 5459 D296 5460 D298 5461 D15 D18 Ar88 5462 D16 5463 D18 5464 D21 5465 D33 5466 D34 5467 D36 5468 D45 5469 D46 5470 D48 5471 D63 5472 D64 5473 D66 5474 D73 5475 D74 5476 D75 5477 D76 5478 D78 5479 D155 5480 D182 5481 D183 5482 D185 5483 D246 5484 D265 5485 D266 5486 D267 5487 D268 5488 D269 5489 D296 5490 D298 5491 D15 D21 5492 D16 5493 D18 5494 D21 5495 D33 5496 D34 5497 D36 5498 D45 5499 D46 5500 D48 5501 D63 5502 D64 5503 D66 5504 D73 5505 D74 5506 D75 5507 D76 5508 D78 5509 D155 5510 D182 5511 D183 5512 D185 5513 D246 5514 D265 5515 D266 5516 D267 5517 D268 5518 D269 5519 D296 5520 D298 5521 D15 D33 Ar88 5522 D16 5523 D18 5524 D21 5525 D33 5526 D34 5527 D36 5528 D45 5529 D46 5530 D48 5531 D63 5532 D64 5533 D66 5534 D73 5535 D74 5536 D75 5537 D76 5538 D78 5539 D155 5540 D182 5541 D183 5542 D185 5543 D246 5544 D265 5545 D266 5546 D267 5547 D268 5548 D269 5549 D296 5550 D298 5551 D15 D34 5552 D16 5553 D18 5554 D21 5555 D33 5556 D34 5557 D36 5558 D45 5559 D46 5560 D48 5561 D63 5562 D64 5563 D66 5564 D73 5565 D74 5566 D75 5567 D76 5568 D78 5569 D155 5570 D182 5571 D183 5572 D185 5573 D246 5574 D265 5575 D266 5576 D267 5577 D268 5578 D269 5579 D296 5580 D298 5581 D15 D36 Ar88 5582 D16 5583 D18 5584 D21 5585 D33 5586 D34 5587 D36 5588 D45 5589 D46 5590 D48 5591 D63 5592 D64 5593 D66 5594 D73 5595 D74 5596 D75 5597 D76 5598 D78 5599 D155 5600 D182 5601 D183 5602 D185 5603 D246 5604 D265 5605 D266 5606 D267 5607 D268 5608 D269 5609 D296 5610 D298 5611 D15 D45 5612 D16 5613 D18 5614 D21 5615 D33 5616 D34 5617 D36 5618 D45 5619 D46 5620 D48 5621 D63 5622 D64 5623 D66 5624 D73 5625 D74 5626 D75 5627 D76 5628 D78 5629 D155 5630 D182 5631 D183 5632 D185 5633 D246 5634 D265 5635 D266 5636 D267 5637 D268 5638 D269 5639 D296 5640 D298 5641 D15 D46 Ar88 5642 D16 5643 D18 5644 D21 5645 D33 5646 D34 5647 D36 5648 D45 5649 D46 5650 D48 5651 D63 5652 D64 5653 D66 5654 D73 5655 D74 5656 D75 5657 D76 5658 D78 5659 D155 5660 D182 5661 D183 5662 D185 5663 D246 5664 D265 5665 D266 5666 D267 5667 D268 5668 D269 5669 D296 5670 D298 5671 D15 D15 5672 D16 5673 D18 5674 D21 5675 D33 5676 D34 5677 D36 5678 D45 5679 D46 5680 D48 5681 D63 5682 D64 5683 D66 5684 D73 5685 D74 5686 D75 5687 D76 5688 D78 5689 D155 5690 D182 5691 D183 5692 D185 5693 D246 5694 D265 5695 D266 5696 D267 5697 D268 5698 D269 5699 D296 5700 D298 5701 D15 D63 Ar88 5702 D16 5703 D18 5704 D21 5705 D33 5706 D34 5707 D36 5708 D45 5709 D46 5710 D48 5711 D63 5712 D64 5713 D66 5714 D73 5715 D74 5716 D75 5717 D76 5718 D78 5719 D155 5720 D182 5721 D183 5722 D185 5723 D246 5724 D265 5725 D266 5726 D267 5727 D268 5728 D269 5729 D296 5730 D298 5731 D15 D64 5732 D16 5733 D18 5734 D21 5735 D33 5736 D34 5737 D36 5738 D45 5739 D46 5740 D48 5741 D63 5742 D64 5743 D66 5744 D73 5745 D74 5746 D75 5747 D76 5748 D78 5749 D155 5750 D182 5751 D183 5752 D185 5753 D246 5754 D265 5755 D266 5756 D267 5757 D268 5758 D269 5759 D296 5760 D298 5761 D15 D66 Ar88 5762 D16 5763 D18 5764 D21 5765 D33 5766 D34 5767 D36 5768 D45 5769 D46 5770 D48 5771 D63 5772 D64 5773 D66 5774 D73 5775 D74 5776 D75 5777 D76 5778 D78 5779 D155 5780 D182 5781 D183 5782 D185 5783 D246 5784 D265 5785 D266 5786 D267 5787 D268 5788 D269 5789 D296 5790 D298 5791 D15 D73 5792 D16 5793 D18 5794 D21 5795 D33 5796 D34 5797 D36 5798 D45 5799 D46 5800 D48 5801 D63 5802 D64 5803 D66 5804 D73 5805 D74 5806 D75 5807 D76 5808 D78 5809 D155 5810 D182 5811 D183 5812 D185 5813 D246 5814 D265 5815 D266 5816 D267 5817 D268 5818 D269 5819 D296 5820 D298 5821 D15 D74 Ar88 5822 D16 5823 D18 5824 D21 5825 D33 5826 D34 5827 D36 5828 D45 5829 D46 5830 D48 5831 D63 5832 D64 5833 D66 5834 D73 5835 D74 5836 D75 5837 D76 5838 D78 5839 D155 5840 D182 5841 D183 5842 D185 5843 D246 5844 D265 5845 D266 5846 D267 5847 D268 5848 D269 5849 D296 5850 D298 5851 D15 D75 5852 D16 5853 D18 5854 D21 5855 D33 5856 D34 5857 D36 5858 D45 5859 D46 5860 D48 5861 D63 5862 D64 5863 D66 5864 D73 5865 D74 5866 D75 5867 D76 5868 D78 5869 D155 5870 D182 5871 D183 5872 D185 5873 D246 5874 D265 5875 D266 5876 D267 5877 D268 5878 D269 5879 D296 5880 D298 5881 D15 D76 Ar88 5882 D16 5883 D18 5884 D21 5885 D33 5886 D34 5887 D36 5888 D45 5889 D46 5890 D48 5891 D63 5892 D64 5893 D66 5894 D73 5895 D74 5896 D75 5897 D76 5898 D78 5899 D155 5900 D182 5901 D183 5902 D185 5903 D246 5904 D265 5905 D266 5906 D267 5907 D268 5908 D269 5909 D296 5910 D298 5911 D15 D78 5912 D16 5913 D18 5914 D21 5915 D33 5916 D34 5917 D36 5918 D45 5919 D46 5920 D48 5921 D63 5922 D64 5923 D66 5924 D73 5925 D74 5926 D75 5927 D76 5928 D78 5929 D155 5930 D182 5931 D183 5932 D185 5933 D246 5934 D265 5935 D266 5936 D267 5937 D268 5938 D269 5939 D296 5940 D298 5941 D15 D155 Ar88 5942 D16 5943 D18 5944 D21 5945 D33 5946 D34 5947 D36 5948 D45 5949 D46 5950 D48 5951 D63 5952 D64 5953 D66 5954 D73 5955 D74 5956 D75 5957 D76 5958 D78 5959 D155 5960 D182 5961 D183 5962 D185 5963 D246 5964 D265 5965 D266 5966 D267 5967 D268 5968 D269 5969 D296 5970 D298 5971 D15 D182 5972 D16 5973 D18 5974 D21 5975 D33 5976 D34 5977 D36 5978 D45 5979 D46 5980 D48 5981 D63 5982 D64 5983 D66 5984 D73 5985 D74 5986 D75 5987 D76 5988 D78 5989 D155 5990 D182 5991 D183 5992 D185 5993 D246 5994 D265 5995 D266 5996 D267 5997 D268 5998 D269 5999 D296 6000 D298 6001 D15 D183 Ar88 6002 D16 6003 D18 6004 D21 6005 D33 6006 D34 6007 D36 6008 D45 6009 D46 6010 D48 6011 D63 6012 D64 6013 D66 6014 D73 6015 D74 6016 D75 6017 D76 6018 D78 6019 D155 6020 D182 6021 D183 6022 D185 6023 D246 6024 D265 6025 D266 6026 D267 6027 D268 6028 D269 6029 D296 6030 D298 6031 D15 D185 6032 D16 6033 D18 6034 D21 6035 D33 6036 D34 6037 D36 6038 D45 6039 D46 6040 D48 6041 D63 6042 D64 6043 D66 6044 D73 6045 D74 6046 D75 6047 D76 6048 D78 6049 D155 6050 D182 6051 D183 6052 D185 6053 D246 6054 D265 6055 D266 6056 D267 6057 D268 6058 D269 6059 D296 6060 D298 6061 D15 D246 Ar88 6062 D16 6063 D18 6064 D21 6065 D33 6066 D34 6067 D36 6068 D45 6069 D46 6070 D48 6071 D63 6072 D64 6073 D66 6074 D73 6075 D74 6076 D75 6077 D76 6078 D78 6079 D155 6080 D182 6081 D183 6082 D185 6083 D246 6084 D265 6085 D266 6086 D267 6087 D268 6088 D269 6089 D296 6090 D298 6091 D15 D265 6092 D16 6093 D18 6094 D21 6095 D33 6096 D34 6097 D36 6098 D45 6099 D46 6100 D48 6101 D63 6102 D64 6103 D66 6104 D73 6105 D74 6106 D75 6107 D76 6108 D78 6109 D155 6110 D182 6111 D183 6112 D185 6113 D246 6114 D265 6115 D266 6116 D267 6117 D268 6118 D269 6119 D296 6120 D298 6121 D15 D266 Ar88 6122 D16 6123 D18 6124 D21 6125 D33 6126 D34 6127 D36 6128 D45 6129 D46 6130 D48 6131 D63 6132 D64 6133 D66 6134 D73 6135 D74 6136 D75 6137 D76 6138 D78 6139 D155 6140 D182 6141 D183 6142 D185 6143 D246 6144 D265 6145 D266 6146 D267 6147 D268 6148 D269 6149 D296 6150 D298 6151 D15 D267 6152 D16 6153 D18 6154 D21 6155 D33 6156 D34 6157 D36 6158 D45 6159 D46 6160 D48 6161 D63 6162 D64 6163 D66 6164 D73 6165 D74 6166 D75 6167 D76 6168 D78 6169 D155 6170 D182 6171 D183 6172 D185 6173 D246 6174 D265 6175 D266 6176 D267 6177 D268 6178 D269 6179 D296 6180 D298 6181 D15 D268 Ar88 6182 D16 6183 D18 6184 D21 6185 D33 6186 D34 6187 D36 6188 D45 6189 D46 6190 D48 6191 D63 6192 D64 6193 D66 6194 D73 6195 D74 6196 D75 6197 D76 6198 D78 6199 D155 6200 D182 6201 D183 6202 D185 6203 D246 6204 D265 6205 D266 6206 D267 6207 D268 6208 D269 6209 D296 6210 D298 6211 D15 D269 6212 D16 6213 D18 6214 D21 6215 D33 6216 D34 6217 D36 6218 D45 6219 D46 6220 D48 6221 D63 6222 D64 6223 D66 6224 D73 6225 D74 6226 D75 6227 D76 6228 D78 6229 D155 6230 D182 6231 D183 6232 D185 6233 D246 6234 D265 6235 D266 6236 D267 6237 D268 6238 D269 6239 D296 6240 D298 6241 D15 D296 Ar88 6242 D16 6243 D18 6244 D21 6245 D33 6246 D34 6247 D36 6248 D45 6249 D46 6250 D48 6251 D63 6252 D64 6253 D66 6254 D73 6255 D74 6256 D75 6257 D76 6258 D78 6259 D155 6260 D182 6261 D183 6262 D185 6263 D246 6264 D265 6265 D266 6266 D267 6267 D268 6268 D269 6269 D296 6270 D298 6271 D15 D298 6272 D16 6273 D18 6274 D21 6275 D33 6276 D34 6277 D36 6278 D45 6279 D46 6280 D48 6281 D63 6282 D64 6283 D66 6284 D73 6285 D74 6286 D75 6287 D76 6288 D78 6289 D155 6290 D182 6291 D183 6292 D185 6293 D246 6294 D265 6295 D266 6296 D267 6297 D268 6298 D269 6299 D296 6300 D298

Compounds derived from compounds 1 to 6300 by substituting H of R¹ with D are disclosed herein as compounds 6301 to 12600, respectively, herein. Compounds derived from 1 to 6300 by exchanging R¹ and R⁴ to R⁴ and R¹, respectively are disclosed herein as compounds 12601 to 18900. Compounds derived from compounds 12601 to 18900 by substituting H of R² with D are disclosed herein as compounds 18901 to 25200, respectively. Compounds derived from compounds 1 to 6300 by changing R¹. R², R³ and R⁴ to R³, R¹, R⁴ and R², respectively, are disclosed herein as compounds 25201 to 31500. Compounds derived from compounds 25201 to 31500 by substituting H of R³ with D are disclosed herein as compounds 31501 to 37800, respectively. Compounds derived from compounds 1 to 6300 by changing R¹, R², R³ and R⁴ to R⁴, R¹, R² and R³, respectively, are disclosed herein as compounds 37801 to 44100. Compounds derived from compounds 37801 to 44100 by substituting H of R⁴ with D are disclosed herein as compounds 44101 to 50400, respectively. Compounds derived from compounds 1 to 6300 by changing R¹, R³ and R⁴ to R³, R⁴ and R¹, respectively, are disclosed herein as compounds 50401 to 56700, respectively. Compounds derived from compounds 50401 to 56700 by substituting H of R³ with D are disclosed herein as compounds 56701 to 63000, respectively. Compounds derived from compounds 1 to 6300 by exchanging R³ and R⁴ to R⁴ and R³, respectively, are disclosed herein as compounds 63001 to 69300, respectively. Compounds derived from compounds 63001 to 69300 by substituting H of R′ with D are disclosed herein as compounds 69301 to 75600, respectively. These compounds 1 to 75600 are individually specified in point of the structures thereof, and are described as specific compounds in the present description.

The molecular weight of the compound represented by the general formula (1) is, for example, when an organic layer containing the compound represented by the general formula (1) is intended to be formed by an evaporation method and used, preferably 1500 or less, more preferably 1200 or less, even more preferably 1000 or less, further more preferably 900 or less. The lower limit of the molecular weight is a molecular weight of the smallest compound represented by the general formula (1). Preferably, the lower limit is 624 or more.

The compound represented by the general formula (1) can be formed into a layer by a coating method, irrespective of the molecular weight thereof. A coating method can form the compound having a relatively large molecular weight into a layer. The compound represented by the general formula (1) has an advantage that, among cyanobenzene compounds, the compound is readily soluble in an organic compound. Consequently, a coating method is readily applicable to the compound represented by the general formula (1) and, in addition, the compound can be purified to have an increased purity.

By applying the present invention, it is considered that a compound containing plural number of structures represented by the general formula (1) in the molecule can be used as a light emitting material.

For example, it is considered that a polymerizable group is previously introduced into the structure represented by the general formula (1), and the polymer formed by polymerizing the polymerizable group is used as a light emitting material. Specifically, it is considered that a monomer containing a polymerizable functional group in any of Ar, D¹ and D² in the general formula (1) is prepared, and this is homo-polymerized, or is copolymerized with any other monomer to give a polymer having a repeating unit, and the polymer is used as alight emitting material. Or it is also considered that compounds each having the structure represented by the general formula (1) are coupled to give a dimer or a trimer, and these are used as a light emitting material.

Examples of the polymer having a repeating unit that contains the structure represented by the general formula (1) include polymers having a structure represented by the following general formula (4) or (5).

In the general formula (4) or (5), Q represents a group containing the structure represented by the general formula (1). L¹ and L² each represent a linking group. The carbon number of the linking group is preferably 0 to 20, more preferably 1 to 15, even more preferably 2 to 10. The linking group preferably has a structure represented by —X¹¹-L¹¹-. Here. X¹¹ represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom. L¹¹ represents a linking group, and is preferably a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group, more preferably a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenylene group.

In the general formula (4) or (5), R¹⁰¹, R¹⁰², R¹⁰³ and R¹⁰⁴ each independently represent a substituent. Preferably, they each are a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or a halogen atom, more preferably an unsubstituted alkyl group having 1 to 3 carbon atoms, an unsubstituted alkoxy group having 1 to 3 carbon atoms, a fluorine atom or a chlorine atom, even more preferably an unsubstituted alkyl group having 1 to 3 carbon atoms or an unsubstituted alkoxy group having 1 to 3 carbon atoms.

The linking group represented by L¹ and L² bonds to any of Ar. D¹ and D² in formula (1) that constitutes Q. Two or more linking groups can bond to one Q to form a crosslinked structure or a network structure.

Examples of specific structures of the repeating unit include structures represented by the following formulae (6) to (9).

Polymers having a repeating unit that contains any of these formulae (6) to (9) can be synthesized by previously introducing a hydroxy group into any of Ar, D¹ and D² in the general formula (1), then reacting the group serving as a linker with the following compound to thereby introduce a polymerizable group, and polymerizing the polymerizable group.

The polymer having a structure represented by the general formula (1) in the molecule can be a polymer having only a repeating unit that has the structure represented by the general formula (1), or can be a polymer containing a repeating unit that has any other structure. The repeating unit having the structure represented by the general formula (1) to be contained in the polymer may be a single kind or two or more kinds. The repeating unit not having the structure of the general formula (1) includes those derived from monomers used in general copolymerization. For example, it includes repeating units derived from monomers having an ethylenically unsaturated bond, such as ethylene or styrene.

In some embodiments, the compound represented by the general formula (1) is a light emitting material.

In some embodiments, the compound represented by the general formula (1) is a compound that can emit delayed fluorescence.

In some embodiments of the present disclosure, the compound represented by the general formula (1) is, when excited thermally or by an electronic means, able to emit light in a UV region, in a blue, green, yellow, orange or red region in a visible spectrum (e.g., about 420 nm to about 500 nm, about 500 nm to about 600 nm, or about 600 nm to about 700 nm) or in a near IR region.

In some embodiments of the present disclosure, the compound represented by the general formula (1) is, when excited thermally or by an electronic means, able to emit light in a red or orange region in a visible spectrum (e.g., about 620 nm to about 780 nm, about 650 nm).

In some embodiments of the present disclosure, the compound represented by the general formula (1) is, when excited thermally or by an electronic means, able to emit light in an orange or yellow region in a visible spectrum (e.g., about 570 nm to about 620 nm, about 590 nm, about 570 nm).

In some embodiments of the present disclosure, the compound represented by the general formula (1) is, when excited thermally or by an electronic means, able to emit light in a green region in a visible spectrum (e.g., about 490 nm to about 575 nm, about 510 nm).

In some embodiments of the present disclosure, the compound represented by the general formula (1) is, when excited thermally or by an electronic means, able to emit light in a blue region in a visible spectrum (e.g., about 400 nm to about 490 nm, about 475 nm).

In some embodiments of the present disclosure, the compound represented by the general formula (1) is, when excited thermally or by an electronic means, able to emit light in a UV spectral region (e.g., about 280 to 400 nm).

In some embodiments of the present disclosure, the compound represented by the general formula (1) is, when excited thermally or by an electronic means, able to emit light in an IR spectral region (e.g., about 780 nm to 2 μm).

Electronic characteristics of small-molecule chemical substance libraries can be calculated by known ab initio quantum chemistry calculation. For example, according to time-dependent density functional theory using 6-31G* as a basis, and a functional group known as Becke's three parameters, Lee-Yang-Parr hybrid functionals, the Hartree-Fock equation (TD-DFT/B3LYP/6-31G*) is analyzed and molecular fractions (parts) having HOMO not lower than a specific threshold value and LUMO not higher than a specific threshold value can be screened.

With that, for example, in the presence of a HOMO energy (for example, ionizing potential) of −6.5 eV or more, a donor part (“D”) can be selected. On the other hand, for example, in the presence of a LUMO energy (for example, electron affinity) of −0.5 eV or less, an acceptor part (“A”) can be selected. A bridge part (“B”) is a strong conjugated system, for example, capable of strictly limiting the acceptor part and the donor part in a specific three-dimensional configuration, and therefore prevents the donor part and the acceptor part from overlapping in the n-conjugated system.

In some embodiments, a compound library is screened using at least one of the following characteristics.

1. Light emission around a specific wavelength.

2. A triplet state over a calculated specific energy level.

3. ΔE_(ST) value lower than a specific value.

4. Quantum yield more than a specific value.

5. HOMO level.

6. LUMO level.

In some embodiments, the difference (ΔE_(ST)) between the lowest singlet excited state and the lowest triplet excited state at 77 K is less than about 0.5 eV, less than about 0.4 eV, less than about 0.3 eV, less than about 0.2 eV, or less than about 0.1 eV. In some embodiments, ΔE_(ST) value is less than about 0.09 eV, less than about 0.08 eV, less than about 0.07 eV, less than about 0.06 eV, less than about 0.05 eV, less than about 0.04 eV, less than about 0.03 eV, less than about 0.02 eV, or less than about 0.01 eV.

In some embodiments, the compound represented by the general formula (1) shows a quantum yield of more than 25%, for example, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95% or more.

[Synthesis Method for Compound Represented by General Formula (1)]

The compound represented by the general formula (1) is a novel compound.

The compound represented by the general formula (1) can be synthesized by combining known reactions. For example, the compound can be synthesized by reacting a difluoroisophthalonitrile, where the positions to which D¹ and D² are introduced are substituted with fluorine atoms, with D¹-H and D²-H in the presence of sodium hydride in tetrahydrofuran. In the case where D¹-H and D²-H differ, the reaction with D¹-H and D²-H can be carried out in two stages. For the specific conditions and the reaction process, reference can be made to Synthesis Examples given hereinafter.

[Structure Using Compound Represented by General Formula (1)]

In some embodiments, the compound represented by the general formula (1) is used along with at least one material which is combined with the compound, in which the compound is dispersed, which bonds to the compound in a mode of covalent bonding, which is coated with the compound, which carries the compound or which associates with the compound (for example, small molecules, polymers, metals, metal complexes), and forms a solid film or layer. For example, the compound represented by the general formula (1) can be combined with an electroactive material to form a film. In some cases, the compound represented by the general formula (1) can be combined with a hole transporting polymer. In some cases, the compound represented by the general formula (1) can be combined with an electron transporting polymer. In some cases, the compound represented by the general formula (1) can be combined with a hole transporting polymer and an electron transporting polymer. In some cases, the compound represented by the general formula (1) can be combined with a copolymer having both a hole transporting moiety and an electron transporting moiety. In the above-mentioned embodiments, the electrons and/or holes formed in a solid film or layer can be interacted with the compound represented by the general formula (1).

[Film Formation]

In some embodiments, a film containing the compound represented by the general formula (1) can be formed in a wet process. In the wet process, a solution prepared by dissolving a composition containing the compound of the present invention is applied onto a surface, and then the solvent is removed to form a film. The wet process includes a spin coating method, a slit coating method, an ink jet method (a spraying method), a gravure printing method, an offset printing method and flexographic printing method, which, however are not limitative. In the wet process, an appropriate organic solvent capable of dissolving a composition containing the compound of the present invention is selected and used. In some embodiments, a substituent (for example, an alkyl group) capable of increasing the solubility in an organic solvent can be introduced into the compound contained in composition.

In some embodiments, a film containing the compound of the present invention can be formed in a dry process. In some embodiments, a vacuum evaporation method is employable as a dry process, which, however, is not limitative. In the case where a vacuum evaporation method is employed, compounds to constitute a film can be co-evaporated from individual evaporation sources, or can be co-evaporated from a single evaporation source formed by mixing the compounds. In the case where a single evaporation source is used, a mixed powder prepared by mixing compound powders can be used, or a compression molded body prepared by compression-molding the mixed powder can be used, or a mixture prepared by heating and melting the constituent compounds and cooling the resulting melt can be used. In some embodiments, by co-evaporation under the condition where the evaporation rate (weight reduction rate) of the plural compounds contained in a single evaporation source is the same or is nearly the same, a film having a compositional ratio corresponding to the compositional ratio of the plural compounds contained in the evaporation source can be formed. When plural compounds are mixed in the same compositional ratio as the compositional ratio of the film to be formed to prepare an evaporation source, a film having a desired compositional ratio can be formed in a simplified manner. In some embodiments, the temperature at which the compounds to be co-evaporated has the same weight reduction ratio is specifically defined, and the temperature can be employed as the temperature of co-evaporation.

Use Examples of Compound Represented by General Formula (1) Organic Light Emitting Diode:

One embodiment of the present invention relates to use of the compound represented by the general formula (1) of the present invention as a light emitting material for organic light emitting devices. In some embodiments, the compound represented by the general formula (1) of the present invention can be effectively used as a light emitting material in a light emitting layer in an organic light emitting device. In some embodiments, the compound represented by the general formula (1) of the present invention includes delayed fluorescence (delayed fluorescent material) that emits delayed fluorescence. In some embodiments, the present invention provides a delayed fluorescent material having a structure represented by the general formula (1). In some embodiments, the present invention relates to use of the compound represented by the general formula (1) of the present invention as a delayed fluorescent material. In some embodiments, the compound represented by the general formula (1) of the present invention can be used as a host material, and can be used along with one or more light emitting materials, in which the light emitting material can be a fluorescent material, a phosphorescent material or TADF. In some embodiments, the compound represented by the general formula (1) can also be used as a hole transporting material. In some embodiments, the compound represented by the general formula (1) can be used as an electron transporting material. In some embodiments, the present invention relates to a method of generating delayed fluorescence from the compound represented by the general formula (1). In some embodiments, an organic light emitting device containing a compound as a light emitting material emits delayed fluorescence and exhibits high luminous radiation efficiency.

In some embodiments, the light emitting layer contains the compound represented by the general formula (1), and the compound represented by the general formula (1) is aligned in parallel to the substrate. In some embodiment, the substrate is a film-forming surface. In some embodiment, the alignment of the compound represented by the general formula (1) relative to the film-forming surface can have some influence on the propagation direction of light emitted by the aligned compounds, or can determine the direction. In some embodiments, by aligning the propagation direction of light emitted by the compound represented by the general formula (1), the light extraction efficiency from the light emitting layer can be improved.

One embodiment of the present invention relates to an organic light emitting device. In some embodiments, the organic light emitting device includes alight emitting layer. In some embodiments, the light emitting layer contains, as a light emitting material therein, the compound represented by the general formula (1). In some embodiments, the organic light emitting device is an organic photoluminescent device (organic PL device). In some embodiments, the organic light emitting device is an organic electroluminescent device (organic EL device). In some embodiments, the compound represented by the general formula (1) assists light irradiation from the other light emitting materials contained in the light emitting layer (as a so-called assist dopant). In some embodiments, the compound represented by the general formula (1) contained in the light emitting layer is in a lowest excited singlet energy level, and is contained between the lowest excited singlet energy level of the host material contained in the light emitting layer and the lowest excited singlet energy level of the other light emitting materials contained in the light emitting layer.

In some embodiments, the organic photoluminescent device contains at least one light emitting layer. In some embodiments, the organic electroluminescent device comprises at least an anode, a cathode, and an organic layer between the anode and the cathode. In some embodiments, the organic laver comprises at least a light emitting layer. In some embodiments, the organic layer comprises only a light emitting layer. In some embodiments, the organic layer, comprises one or more organic layers in addition to the light emitting layer. Examples of the organic layer include a hole transporting layer, a hole injection layer, an electron barrier layer, a hole barrier layer, an electron injection layer, an electron transporting layer and an exciton barrier layer. In some embodiments, the hole transporting layer may be a hole injection and transporting layer having a hole injection function, and the electron transporting layer may be an electron injection and transporting layer having an electron injection function. An example of an organic electroluminescent device is shown in FIG. 1 .

Light Emitting Layer:

In some embodiments, the light emitting layer is a layer where holes and electrons injected from the anode and the cathode, respectively, are recombined to form excitons. In some embodiments, the layer emits light.

In some embodiments, only a light emitting material is used as the light emitting layer. In some embodiments, the light emitting layer contains a light emitting material and a host material. In some embodiments, the light emitting material is at least one compound represented by the general formula (1). In some embodiments, for improving luminous radiation efficiency of an organic electroluminescent device and an organic photoluminescence device, the singlet exciton and the triplet exciton generated in a light emitting material is confined inside the light emitting material. In some embodiments, a host material is used in the light emitting layer in addition to a light emitting material therein. In some embodiments, the host material is an organic compound. In some embodiments, the organic compound has an excited singlet energy and an excited triplet energy, and at least one of them is higher than those in the light emitting material of the present invention. In some embodiments, the singlet exciton and the triplet exciton generated in the light emitting material of the present invention are confined in the molecules of the light emitting material of the present invention. In some embodiments, the singlet and triplet excitons are fully confined for improving luminous radiation efficiency. In some embodiments, although high luminous radiation efficiency is still attained, singlet excitons and triplet excitons are not fully confined, that is, a host material capable of attaining high luminous radiation efficiency can be used in the present invention with no specific limitation. In some embodiments, in the light emitting material in the light emitting layer of the device of the present invention, luminous radiation occurs. In some embodiments, radiated light includes both fluorescence and delayed fluorescence. In some embodiments, radiated light includes radiated light from a host material. In some embodiments, radiated light is composed of radiated light from a host material. In some embodiments, radiated light includes radiated light from the compound represented by the general formula (1), and radiated light from a host material. In some embodiment, a TADF molecule and a host material are used. In some embodiments, TADF is an assist dopant.

When the compound represented by the general formula (1) is used as an assist dopant, various compounds can be employed as a light emitting material (preferably a fluorescent material). Such light emitting materials include an anthracene derivative, a tetracene derivative, a naphthacene derivative, a pyrene derivative, a perylene derivative, a chrysene derivative, a rubrene derivative, a coumarin derivative, a pyran derivative, a stilbene derivative, a fluorene derivative, an anthryl derivative, a pyrromethene derivative, a terphenyl derivative, a terphenylene derivative, a fluoranthene derivative, an amine derivative, a quinacridone derivative, an oxadiazole derivative, a malononitrile derivative, a pyran derivative, a carbazole derivative, a julolidine derivative, a thiazole derivative, and a derivative having a metal (Al or Zn). These exemplified skeletons may have a substituent or may not have a substituent. These exemplified skeletons can be combined with each other.

In the following, examples of light emitting materials that can be combined with the assist dopant represented by the general formula (1) are shown for use herein.

Also the compounds described in WO2015/022974, paragraphs 0220 to 0239 can be especially favorably employed as a light emitting material for use along with the assist dopant represented by the general formula (1).

In some embodiments where a host material is used, the amount of the compound of the present invention contained in the light emitting layer as a light emitting material therein is 0.1% by weight or more. In some embodiments where a host material is used, the amount of the compound of the present invention contained in the light emitting layer as a light emitting material therein is 1% by weight or more. In some embodiments where a host material is used, the amount of the compound of the present invention contained in the light emitting layer as a light emitting material therein is 50% by weight or less. In some embodiments where a host material is used, the amount of the compound of the present invention contained in the light emitting layer as a light emitting material therein is 20% by weight or less. In some embodiments where a host material is used, the amount of the compound of the present invention contained in the light emitting layer as a light emitting material therein is 10% by weight or less.

In some embodiments, the host material in the light emitting layer is an organic compound having a hole transporting function and an electron transporting function. In some embodiments, the host material in the light emitting layer is an organic compound that prevents the wavelength of the emitted light from increasing. In some embodiments, the host material in the light emitting layer is an organic compound having a high glass transition temperature.

In some embodiments, the host material is selected from the group consisting of

In some embodiments, the light emitting layer contains at least two TADF molecules differing in the structure. For example, the light emitting layer can contain three kinds of materials, a host material, a first TADF molecule and a second TADF molecule whose excited singlet energy level is higher in that order. At that time, the first TADF molecule and the second TADF molecule are preferably such that the difference of ΔE_(ST) between the lowest excited singlet energy level and the lowest excited triplet energy level at 77 K thereof is 0.3 eV or less, more preferably 0.25 eV or less, even more preferably 0.2 eV or less, further more preferably 0.15 eV or less, further more preferably 0.1 eV or less, further more preferably 0.07 eV or less, further more preferably 0.05 eV or less, further more preferably 0.03 eV or less, especially preferably 0.01 eV or less. The content of the first TADF molecule in the light emitting layer is preferably larger than the content of the second TADF molecule therein. The content of the host material in the light emitting layer is preferably larger than the content of the second TADF molecule therein. The content of the first TADF molecule in the light emitting layer can be larger than the content of the host material therein, or can be smaller than or the same as the latter. In some embodiments, the composition in the light emitting layer can be 10 to 70% by weight of the host material, 10 to 80% by weight of the TADF molecule, and 0.1 to 30% by weight of the second TADF molecule. In some embodiments, the composition in the light emitting layer can be 20 to 45% by weight of the host material, 50 to 75% by weight of the first TADF molecule, and 5 to 20% by weight of the second TADF molecule. In some embodiments, the photoluminescence quantum yield φPL1(A) by photoexcitation of the co-deposited film of the first TADF molecule and the host material (the content of the first TADF molecule in the co-deposited film=A % by weight) and the photoluminescence quantum yield φPL2(A) by photoexcitation of the co-deposited film of the second TADF molecule and the host material (the content of the second TADF molecule in the co-deposited film=A % by weight) satisfy a relational formula φPL1(A)>φPL2(A). In some embodiments, the photoluminescence quantum yield φPL2(B) by photoexcitation of the co-deposited film of the second TADF molecule and the host material (the content of the second TADF molecule in the co-deposited film=A % by weight) and the photoluminescence quantum yield φPL2(100) by photoexcitation of the single film of the second TADF molecule satisfy a relational formula φPL2(B)>φPL2(100). In some embodiments, the light emitting layer can contain three TADF molecules differing in the structure. The compound of the present invention can be any of plural TADF compounds contained in the light emitting layer.

In some embodiments, the light emitting layer can be composed of a material selected from the group consisting of a host material, an assist dopant and a light emitting material. In some embodiments, the light emitting layer does not contain a metal element. In some embodiments, the light emitting layer can be composed of a material composed of atoms alone selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, an oxygen atom and a sulfur atom. Or the light emitting layer can also be composed of a material composed of atoms alone selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom a nitrogen atom and an oxygen atom. Or the light emitting layer can also be composed of a material composed of atoms alone selected from the group consisting of a carbon atom a hydrogen atom, a nitrogen atom and an oxygen atom.

When the light emitting layer contains a TADF material except the compound of the present invention, the TADF material can be a known delayed fluorescent material. Preferred delayed fluorescent materials are compounds included in the general formulae described in WO2013/154064, paragraphs 0008 to 0048 and 0095 to 0133; WO2013/011954, paragraphs 0007 to 0047 and 0073 to 0085; WO2013/011955, paragraphs 0007 to 0033 and 0059 to 0066; WO2013/081088, paragraphs 0008 to 0071 and 0118 to 0133; JP2013-256490A, paragraphs 0009 to 0046 and 0093 to 0134; JP2013-116975A, paragraphs 0008 to 0020 and 0038 to 0040; WO2013/133359, paragraphs 0007 to 0032 and 0079 to 0084: WO2013/161437, paragraphs 0008 to 0054 and 0101 to 0121; JP2014-9352A, paragraphs 0007 to 0041 and 0060 to 0069; and JP2014-9224A, paragraphs 0008 to 0048 and 0067 to 0076: JP2017-119663A, paragraphs 0013 to 0025; JP2017-119664A, paragraphs 0013 to 0026; JP2017-222623A, paragraphs 0012 to 0025; JP2017-226838A, paragraphs 0010 to 0050; JP2018-100411A, paragraphs 0012 to 0043; WO2018/047853, paragraphs 0016 to 0044; and exemplary compounds therein capable of emitting delayed fluorescence are especially preferred. In addition, light emitting materials capable of emitting delayed fluorescence, as described in JP2013-253121A. WO2013/133359, WO2014/034535, WO2014/115743, WO2014/122895, WO2014/126200, WO2014/136758, WO2014/133121, WO2014/136860, WO2014/196585, WO2014/189122, WO2014/168101, WO2015/008580, WO2014/203840, WO2015/002213, WO2015/016200, WO2015/019725, WO2015/072470, WO2015/108049, WO2015/080182, WO2015/072537, WO2015/080183, JP2015-129240A, WO2015/129714, WO2015/129715, WO2015/133501, WO2015/136880, WO2015/137244, WO2015/137202, WO2015/137136, WO2015/146541 and WO2015/159541, are preferably employed. These patent publications described in this paragraph are hereby incorporated as a part of this description by reference.

In the following, the constituent members and the other layers than the light emitting layer of the organic electroluminescent device are described.

Substrate.

In some embodiments, the organic electroluminescent device of the invention is supported by a substrate, wherein the substrate is not particularly limited and may be any of those that have been commonly used in an organic electroluminescent device, for example those formed of glass, transparent plastics, quartz and silicon.

Anode

In some embodiments, the anode of the organic electroluminescent device is made of a metal, an alloy, an electroconductive compound, or a combination thereof. In some embodiments, the metal, alloy, or electroconductive compound has a large work function (4 eV or more). In some embodiments, the metal is Au. In some embodiments, the electroconductive transparent material is selected from CuI, indium tin oxide (ITO), SnO₂, and ZnO. In some embodiments, an amorphous material capable of forming a transparent electroconductive film, such as IDIXO (In₂O₃—ZnO), is be used. In some embodiments, the anode is a thin film. In some embodiments the thin film is made by vapor deposition or sputtering. In some embodiments, the film is patterned by a photolithography method. In some embodiments, where the pattern may not require high accuracy (for example, approximately 100 μm or more), the pattern may be formed with a mask having a desired shape on vapor deposition or sputtering of the electrode material. In some embodiments, when a material can be applied as a coating, such as an organic electroconductive compound, a wet film forming method, such as a printing method and a coating method is used. In some embodiments, when the emitted light goes through the anode, the anode has a transmittance of more than 10%, and the anode has a sheet resistance of several hundred Ohm per square or less. In some embodiments, the thickness of the anode is from 10 to 1,000 nm. In some embodiments, the thickness of the anode is from 10 to 200 nm. In some embodiments, the thickness of the anode varies depending on the material used.

Cathode

In some embodiments, the cathode is made of an electrode material a metal having a small work function (4 eV or less) (referred to as an electron injection metal), an alloy, an electroconductive compound, or a combination thereof. In some embodiments, the electrode material is selected from sodium, a sodium-potassium alloy, magnesium, lithium, a magnesium-cupper mixture, a magnesium-silver mixture, a magnesium-aluminum mixture, a magnesium-indium mixture, an aluminum-aluminum oxide (Al₂O₃) mixture, indium, a lithium-aluminum mixture, and a rare earth metal. In some embodiments, a mixture of an electron injection metal and a second metal that is a stable metal having a larger work function than the electron injection metal is used. In some embodiments, the mixture is selected from a magnesium-silver mixture, a magnesium-aluminum mixture, a magnesium-indium mixture, an aluminum-aluminum oxide (Al₂O₃) mixture, a lithium-aluminum mixture, and aluminum. In some embodiments, the mixture increases the electron injection property and the durability against oxidation. In some embodiments, the cathode is produced by forming the electrode material into a thin film by vapor deposition or sputtering. In some embodiments, the cathode has a sheet resistance of several hundred Ohm per square or less. In some embodiments, the thickness of the cathode ranges from 10 nm to 5 sm. In some embodiments, the thickness of the cathode ranges from 50 to 200 nm. In some embodiments, for transmitting the emitted light, any one of the anode and the cathode of the organic electroluminescent device is transparent or translucent. In some embodiments, the transparent or translucent electroluminescent devices enhances the light emission luminance.

In some embodiments, the cathode is formed with an electroconductive transparent material, as described for the anode, to form a transparent or translucent cathode. In some embodiments, a device comprises an anode and a cathode, both being transparent or translucent.

Injection Layer

An injection layer is a layer between the electrode and the organic layer. In some embodiments, the injection layer decreases the driving voltage and enhances the light emission luminance. In some embodiments the injection layer includes a hole injection layer and an electron injection layer. The injection layer can be positioned between the anode and the light emitting layer or the hole transporting layer, and between the cathode and the light emitting layer or the electron transporting layer. In some embodiments, an injection layer is present. In some embodiments, no injection layer is present.

Preferred compound examples for use as a hole injection material are shown below.

MoO₃,

Next, preferred compound examples for use as an electron injection material are shown below.

Barrier Layer

A barrier layer is a layer capable of inhibiting charges (electrons or holes) and/or excitons present in the light emitting layer from being diffused outside the light emitting layer. In some embodiments, the electron barrier layer is between the light emitting layer and the hole transporting layer, and inhibits electrons from passing through the light emitting layer toward the hole transporting layer. In some embodiments, the hole barrier layer is between the light emitting layer and the electron transporting layer, and inhibits holes from passing through the light emitting layer toward the electron transporting layer. In some embodiments, the barrier layer inhibits excitons from being diffused outside the light emitting layer. In some embodiments, the electron barrier layer and the hole barrier layer are exciton barrier layers. As used herein, the term “electron barrier layer” or “exciton barrier layer” includes a layer that has the functions of both electron barrier layer and of an exciton barrier layer.

Hole Barrier Layer

A hole barrier layer acts as an electron transporting layer. In some embodiments, the hole barrier layer inhibits holes from reaching the electron transporting layer while transporting electrons. In some embodiments, the hole barrier layer enhances the recombination probability of electrons and holes in the light emitting layer. The material for the hole barrier layer may be the same materials as the ones described for the electron transporting layer.

Preferred compound examples for use for the hole barrier layer are shown below.

Electron Barrier Layer

As electron barrier layer transports holes. In some embodiments, the electron barrier layer inhibits electrons from reaching the hole transporting layer while transporting holes. In some embodiments, the electron barrier layer enhances the recombination probability of electrons and holes in the light emitting layer.

Preferred compound examples for use as the electron barrier material are shown below.

Exciton Barrier Layer

An exciton barrier layer inhibits excitons generated through recombination of holes and electrons in the light emitting layer from being diffused to the charge transporting layer. In some embodiments, the exciton barrier layer enables effective confinement of excitons in the light emitting layer. In some embodiments, the light emission efficiency of the device is enhanced. In some embodiments, the exciton barrier layer is adjacent to the light emitting layer on any of the side of the anode and the side of the cathode, and on both the sides. In some embodiments, where the exciton barrier layer is on the side of the anode, the layer can be between the hole transporting layer and the light emitting layer and adjacent to the light emitting layer. In some embodiments, where the exciton barrier layer is on the side of the cathode, the layer can be between the light emitting layer and the cathode and adjacent to the light emitting layer. In some embodiments, a hole injection layer, an electron barrier layer, or a similar layer is between the anode and the exciton barrier layer that is adjacent to the light emitting layer on the side of the anode. In some embodiments, a hole injection layer, an electron barrier layer, a hole barrier layer, or a similar layer is between the cathode and the exciton barrier layer that is adjacent to the light emitting layer on the side of the cathode. In some embodiments, the exciton barrier layer comprises excited singlet energy and excited triplet energy, at least one of which is higher than the excited singlet energy and the excited triplet energy of the light emitting material, respectively.

Hole Transporting Layer

The hole transporting layer comprises a hole transporting material. In some embodiments, the hole transporting layer is a single layer. In some embodiments, the hole transporting layer comprises a plurality layers.

In some embodiments, the hole transporting material has one of injection or transporting property of holes and barrier property of electrons. In some embodiments, the hole transporting material is an organic material. In some embodiments, the hole transporting material is an inorganic material. Examples of known hole transporting materials that may be used herein include but are not limited to a triazole derivative, an oxadiazole derivative, an imidazole derivative, a carbazole derivative, an indolocarbazole derivative, a polyarylalkane derivative, a pyrazoline derivative, a pyrazolone derivative, a phenylenediamine derivative, an arylamine derivative, an amino-substituted chalcone derivative, an oxazole derivative, a styrylanthracene derivative, a fluorenone derivative, a hydrazone derivative, a stilbene derivative, a silazane derivative, an aniline copolymer and an electroconductive polymer oligomer, particularly a thiophene oligomer, or a combination thereof. In some embodiments, the hole transporting material is selected from a porphyrin compound, an aromatic tertiary amine compound, and a styrylamine compound. In some embodiments, the hole transporting material is an aromatic tertiary amine compound. Preferred compound examples for use as the hole transporting material are shown below.

Electron Transporting Layer

The electron transporting layer comprises an electron transporting material. In some embodiments, the electron transporting layer is a single layer. In some embodiments, the electron transporting layer comprises a plurality of layer.

In some embodiments, the electron transporting material needs only to have a function of transporting electrons, which are injected from the cathode, to the light emitting layer. In some embodiments, the electron transporting material also function as a hole barrier material. Examples of the electron transporting layer that may be used herein include but are not limited to a nitro-substituted fluorene derivative, a diphenylquinone derivative, a thiopyran dioxide derivative, carbodiimide, a fluorenylidene methane derivative, anthraquinodimethane, an anthrone derivatives, an azole derivative, an azine derivative, an oxadiazole derivative, or a combination thereof, or a polymer thereof. In some embodiments, the electron transporting material is a thiadiazole derivative, or a quinoxaline derivative. In some embodiments, the electron transporting material is a polymer material. Preferred compound examples for use as the electron transporting material are shown below.

Hereinunder compound examples preferred as a material that can be added to the organic layers are shown. For example, these can be added as a stabilization material

Preferred materials for use in the organic electroluminescent device are specifically shown. However, the materials usable in the invention should not be limitatively interpreted by the following exemplary compounds. Compounds that are exemplified as materials having a specific function can also be used as materials having any other function.

Devices

In some embodiments, an light emitting layer is incorporated into a device. For example, the device includes, but is not limited to an OLED bulb, an OLED lamp, a television screen, a computer monitor, a mobile phone, and a tablet.

In some embodiments, an electronic device comprises an OLED comprising an anode, a cathode, and at least one organic layer comprising a light emitting layer between the anode and the cathode.

In some embodiments, compositions described herein may be incorporated into various light-sensitive or light-activated devices, such as a OLEDs or photovoltaic devices. In some embodiments, the composition may be useful in facilitating charge transfer or energy transfer Within a device and/or as a hole-transport material. The device may be, for example, an organic light emitting diode (OLED), an organic integrated circuit (O-IC), an organic field-effect transistor (O-FET), an organic thin-film transistor (O-TFT), an organic light emitting transistor (O-LET), an organic solar cell (O-SC), an organic optical detector, an organic photoreceptor, an organic field-quench device (O-FQD), a light emitting electrochemical cell (LEC) or an organic laser diode (O-laser).

Bulbs or Lamps

In some embodiments, an electronic device comprises an OLED comprising an anode, a cathode, and at least one organic layer comprising a light emitting layer between the anode and the cathode.

In some embodiments, a device comprises OLEDs that differ in color. In some embodiments, a device comprises an array comprising a combination of OLEDs. In some embodiments, the combination of OLEDs is a combination of three colors (e.g., RGB). In some embodiments, the combination of OLEDs is a combination of colors that are not red, green, or blue (for example, orange and yellow green). In some embodiments, the combination of OLEDs is a combination of two, four, or more colors.

In some embodiments, a device is an OLED light comprising:

a circuit board having a first side with a mounting surface and an opposing second side, and defining at least one aperture:

at least one OLED on the mounting surface, the at least one OLED configured to emanate light, comprising:

-   -   an anode, a cathode, and at least one organic layer comprising a         light emitting layer between the anode and the cathode;

a housing for the circuit board; and

at least one connector arranged at an end of the housing, the housing and the connector defining a package adapted for installation in a light fixture.

In some embodiments, the OLED light comprises a plurality of OLEDs mounted on a circuit board such that light emanates in a plurality of directions. In some embodiments, a portion of the light emanated in a first direction is deflected to emanate in a second direction. In some embodiments, a reflector is used to deflect the light emanated in a first direction.

Displays or Screens

In some embodiments, the compounds of the invention can be used in a screen or a display. In some embodiments, the compounds of the invention are deposited onto a substrate using a process including, but not limited to, vacuum evaporation, deposition, vapor deposition, or chemical vapor deposition (CVD). In some embodiments, the substrate is a photoplate structure useful in a two-sided etch provides a unique aspect ratio pixel. The screen (which may also be referred to as a mask) is used in a process in the manufacturing of OLED displays. The corresponding artwork pattern design facilitates a very steep and narrow tie-bar between the pixels in the vertical direction and a large, sweeping bevel opening in the horizontal direction. This allows the close patterning of pixels needed for high definition displays while optimizing the chemical deposition onto a TFT backplane.

The internal patterning of the pixel allows the construction of a 3-dimensional pixel opening with varying aspect ratios in the horizontal and vertical directions. Additionally, the use of imaged “stripes” or halftone circles within the pixel area inhibits etching in specific areas until these specific patterns are undercut and fall off the substrate. At that point the entire pixel area is subjected to a similar etch rate but the depths are varying depending on the halftone pattern. Varying the size and spacing of the halftone pattern allows etching to be inhibited at different rates within the pixel allowing for a localized deeper etch needed to create steep vertical bevels.

A preferred material for the deposition mask is invar. Invar is a metal alloy that is cold rolled into long thin sheet in a steel mill. Invar cannot be electrodeposited onto a rotating mandrel as the nickel mask. A preferred and more cost feasible method for forming the open areas in the mask used for deposition is through a wet chemical etching.

In some embodiments, a screen or display pattern is a pixel matrix on a substrate. In some embodiments, a screen or display pattern is fabricated using lithography (e.g., photolithography and e-beam lithography). In some embodiments, a screen or display pattern is fabricated using a wet chemical etch. In further embodiments, a screen or display pattern is fabricated using plasma etching.

Methods of Manufacturing Devices Using the Disclosed Compounds

An OLED display is generally manufactured by forming a large mother panel and then cutting the mother panel in units of cell panels. In general, each of the cell panels on the mother panel is formed by forming a thin film transistor (TFT) including an active layer and a source/drain electrode on a base substrate, applying a planarization film to the TFT, and sequentially forming a pixel electrode, a light emitting layer, a counter electrode, and an encapsulation layer, and then is cut from the mother panel.

An OLED display is generally manufactured by forming a large mother panel and then cutting the mother panel in units of cell panels. In general, each of the cell panels on the mother panel is formed by forming a thin film transistor (TFT) including an active layer and a source/drain electrode on a base substrate, applying a planarization film to the TFT, and sequentially forming a pixel electrode, a light emitting layer, a counter electrode, and an encapsulation layer, and then is cut from the mother panel.

In another aspect, provided herein is a method of manufacturing an organic light emitting diode (OLED) display, the method comprising:

forming a barrier layer on a base substrate of a mother panel;

forming a plurality of display units in units of cell panels on the barrier layer;

forming an encapsulation layer on each of the display units of the cell panels:

applying an organic film to an interface portion between the cell panels.

In some embodiments, the barrier layer is an inorganic film formed of, for example, SiNx, and an edge portion of the barrier layer is covered with an organic film formed of polyimide or acryl. In some embodiments, the organic film helps the mother panel to be softly cut in units of the cell panel.

In some embodiments, the thin film transistor (TFT) layer includes a light emitting layer, a gate electrode, and a source/drain electrode. Each of the plurality of display units may include a thin film transistor (TFT) layer, a planarization film formed on the TFT layer, and a light emitting unit formed on the planarization film, wherein the organic film applied to the interface portion is formed of a same material as a material of the planarization film and is formed at a same time as the planarization film is formed. In some embodiments, a light emitting unit is connected to the TFT layer with a passivation layer and a planarization film therebetween and an encapsulation layer that covers and protects the light emitting unit. In some embodiments of the method of manufacturing, the organic film contacts neither the display units nor the encapsulation layer.

Each of the organic film and the planarization film may include any one of polyimide and acryl. In some embodiments, the barrier layer may be an inorganic film. In some embodiments, the base substrate may be formed of polyimide. The method may further include, before the forming of the barrier layer on one surface of the base substrate formed of polyimide, attaching a carrier substrate formed of a glass material to another surface of the base substrate, and before the cutting along the interface portion, separating the carrier substrate from the base substrate. In some embodiments, the OLED display is a flexible display.

In some embodiments, the passivation layer is an organic film disposed on the TFT layer to cover the TFT layer. In some embodiments, the planarization film is an organic film formed on the passivation layer. In some embodiments, the planarization film is formed of polyimide or acryl, like the organic film formed on the edge portion of the barrier layer. In some embodiments, the planarization film and the organic film are simultaneously formed when the OLED display is manufactured. In some embodiments, the organic film may be formed on the edge portion of the barrier layer such that a portion of the organic film directly contacts the base substrate and a remaining portion of the organic film contacts the barrier layer while surrounding the edge portion of the barrier layer.

In some embodiments, the light emitting layer includes a pixel electrode, a counter electrode, and an organic light emitting layer disposed between the pixel electrode and the counter electrode. In some embodiments, the pixel electrode is connected to the source/drain electrode of the TFT layer.

In some embodiments, when a voltage is applied to the pixel electrode through the TFT layer, an appropriate voltage is formed between the pixel electrode and the counter electrode, and thus the organic light emitting layer emits light, thereby forming an image. Hereinafter, an image forming unit including the TFT layer and the light emitting unit is referred to as a display unit.

In some embodiments, the encapsulation layer that covers the display unit and prevents penetration of external moisture may be formed to have a thin film encapsulation structure in which an organic film and an inorganic film are alternately stacked. In some embodiments, the encapsulation layer has a thin film encapsulation structure in which a plurality of thin films are stacked. In some embodiments, the organic film applied to the interface portion is spaced apart from each of the plurality of display units. In some embodiments, the organic film is formed such that a portion of the organic film directly contacts the base substrate and a remaining portion of the organic film contacts the barrier layer while surrounding an edge portion of the barrier layer.

In one embodiment, the OLED display is flexible and uses the soft base substrate formed of polyimide. In some embodiments, the base substrate is formed on a carrier substrate formed of a glass material, and then the carrier substrate is separated.

In some embodiments, the barrier layer is formed on a surface of the base substrate opposite to the carrier substrate. In one embodiment, the barrier layer is patterned according to a size of each of the cell panels. For example, while the base substrate is formed over the entire surface of a mother panel, the barrier layer is formed according to a size of each of the cell panels, and thus a groove is formed at an interface portion between the barrier layers of the cell panels. Each of the cell panels can be cut along the groove.

In some embodiments, the method of manufacture further comprises cutting along the interface portion, wherein a groove is formed in the barrier layer, wherein at least a portion of the organic film is formed in the groove, and wherein the groove does not penetrate into the base substrate. In some embodiments, the TFT layer of each of the cell panels is formed, and the passivation layer which is an inorganic film and the planarization film which is an organic film are disposed on the TFT layer to cover the TFT layer. At the same time as the planarization film formed of, for example, polyimide or acryl is formed, the groove at the interface portion is covered with the organic film formed of, for example, polyimide or acryl. This is to prevent cracks from occurring by allowing the organic film to absorb an impact generated when each of the cell panels is cut along the groove at the interface portion. That is, if the entire barrier layer is entirely exposed without the organic film, an impact generated when each of the cell panels is cut along the groove at the interface portion is transferred to the barrier layer, thereby increasing the risk of cracks. However, in one embodiment, since the groove at the interface portion between the barrier layers is covered with the organic film and the organic film absorbs an impact that would otherwise be transferred to the barrier layer, each of the cell panels may be softly cut and cracks may be prevented from occurring in the barrier layer. In one embodiment, the organic film covering the groove at the interface portion and the planarization film are spaced apart from each other. For example, if the organic film and the planarization film are connected to each other as one layer, since external moisture may penetrate into the display unit through the planarization film and a portion where the organic film remains, the organic film and the planarization film are spaced apart from each other such that the organic film is spaced apart from the display unit.

In some embodiments, the display unit is formed by forming the light emitting unit, and the encapsulation layer is disposed on the display unit to cover the display unit. As such, once the mother panel is completely manufactured, the carrier substrate that supports the base substrate is separated from the base substrate. In some embodiments, when a laser beam is emitted toward the carrier substrate, the carrier substrate is separated from the base substrate due to a difference in a thermal expansion coefficient between the carrier substrate and the base substrate.

In some embodiments, the mother panel is cut in units of the cell panels. In some embodiments, the mother panel is cut along an interface portion between the cell panels by using a cutter. In some embodiments, since the groove at the interface portion along which the mother panel is cut is covered with the organic film, the organic film absorbs an impact during the cutting. In some embodiments, cracks may be prevented from occurring in the barrier layer during the cutting.

In some embodiments, the methods reduce a defect rate of a product and stabilize its quality.

Another aspect is an OLED display including: a barrier layer that is formed on a base substrate; a display unit that is formed on the barrier layer; an encapsulation layer that is formed on the display unit, and an organic film that is applied to an edge portion of the barrier layer.

EXAMPLES

The features of the present invention will be described more specifically with reference to Synthesis Examples and Examples given below. The materials, processes, procedures and the like shown below may be appropriately modified unless they deviate from the substance of the invention. Accordingly, the scope of the invention is not construed as being limited to the specific examples shown below. It should be noted that the light emission characteristics were evaluated using a source meter (available from Keithley Instruments. Inc.: 2400 series), a semiconductor parameter analyzer (available from Agilent Technologies, Inc., E5273A), an optical power meter measurement device (available from Newport Corporation, 1930C), an optical spectroscope (available from Ocean Optics, Inc., USB2000), a spectroradiometer (available from Topcon Corporation, SR-3), and a streak camera (available from Hamamatsu Photonics K.K., Model C4334).

(Synthesis Example 1) Synthesis of Compound C1

In a nitrogen stream atmosphere, potassium carbonate (1.04 g, 7.5 mmol), benzofuro[2,3-c]carbazole (1.61 g, 6.3 mmol) and 4,6-difluoro-5-phenylisophthalonitrile (0.60 g, 2.5 mmol) were reacted in dimethylformamide (20 mL) at 100° C. for 9 hours. Subsequently, this was restored to room temperature, and water and methanol were added to stop the reaction. The precipitated yellow solid was filtered out, and the filtered residue was purified through silica gel column chromatography (toluene) and reprecipitation (toluene/ethanol) to give a yellow solid of a compound C1 (1.33 g, yield 76%).

¹H NMR (400 MHz, CDCl₃, δ): 8.49 (s, 1H), 8.43 (d, J=7.6 Hz, 2H), 7.96-7.91 (m, 4H), 7.70 (d. J=7.6 Hz, 2H), 7.47-7.36 (m, 8H), 7.14-7.11 (m, 2H), 7.10-7.07 (m, 2H), 6.52-6.46 (m, 3H), 6.37 (t, J=7.6 Hz, 2H).

MS (ASAP): 715.34 (M+H⁺). Calcd for C₅₀H₂₆N4O₂: 714.21.

(Synthesis Example 2) Synthesis of Compound C2

Compound C1 (2.40 g, 3.4 mmol), 4-bromobenzonitrile (1.17 g, 5.0 mmol), potassium carbonate (0.93 g, 6.7 mmol), 2-ethylhexanoic acid (0.10 mg, 0.7 mmol), tricyclohexyl phosphine (0.10 g, 0.5 mmol) and dichlorobis(triphenylphosphine)palladium (0.20 g, 0.3 mmol) were dissolved in xylene (30 mL) in a nitrogen stream atmosphere, and stirred at 120° C. for 18 hours. The mixture was restored to room temperature, and a hardly-soluble substance was removed by Celite filtration. The filtrate was concentrated by reduced pressure distillation, and the residue was purified through silica gel column chromatography (chloroform/hexane=2/1) and reprecipitation (toluene/methanol) to give a white solid of a compound C2 (1.90 g, yield 68%).

¹H NMR (400 MHz, CDCl₃, δ): 8.43 (d, J=7.6 Hz, 2H), 8.00-7.92 (m, 8H), 7.70 (d, J=8.0 Hz, 2H), 7.48-7.36 (m, 8H), 7.19 (d, J=8.0 Hz, 2H), 7.14 (d, J=8.0 Hz, 2H), 6.54-6.50 (m, 3H), 6.40 (t, J=7.6 Hz, 2H).

MS (ASAP): 816.45 (M+H⁺). Calcd for C₅₇H₂₉N₅O₂: 815.23.

(Synthesis Example 3) Synthesis of Compound C3

In a nitrogen steam atmosphere, potassium carbonate (1.22 g, 8.8 mmol), benzofuro[2,3-c]carbazole (2.00 g, 7.4 mmol) and 4,6-difluoro-5-phenylisophthalonitrile (0.77 g, 3.0 mmol) were reacted in dimethylformamide (36 mL) at 80° C. for 2 hours. Subsequently, this was restored to room temperature and water was added to stop the reaction. The reaction mixture was separated with chloroform added thereto, and the organic layer was dried with magnesium sulfate. The solvent was removed by reduced-pressure distillation, and the residue was purified through silica gel column chromatography (toluene) to give a yellow solid of a compound C3 (2.25 g, yield 90%).

¹H NMR (400 MHz, CDCl₃, δ): 8.44 (s, 1H), 8.22 (d, J=5.2 Hz, 2H), 7.92 (t, J=7.2 Hz, 2H), 7.88-7.81 (m, 2H), 7.69 (d, J=8.0 Hz, 2H), 7.45-7.40 (m, 2H), 7.38-7.33 (m, 2H), 7.27-7.26 (m, 1H), 7.22 (t, J=8.4 Hz, 1H), 7.07-6.95 (m, 4H), 6.49-6.46 (m, 3H), 6.40-6.36 (m, 2H), 2.56 (d, J=7.2 Hz, 6H).

MS (ASAP): 743.28 [(M+H)⁺, cal. C₅₂H₃₁N₄O₂, 743.24].

(Synthesis Example 4) Synthesis of Compound C4

In a nitrogen stream atmosphere, sodium hydride (0.30 g, 7.5 mmol) and 11-phenyl-11,12-dihydroindolo[2,3-a]carbazole (2.08 g, 6.3 mmol) were stirred in THF (20 mL) at room temperature for 1 hour, then 4,6-difluoro-5-phenylisophthalonitrile (1.50 g, 6.24 mmol) dissolved in tetrahydrofuran (50 mL) was dropwise added thereto. After this was reacted at room temperature for 5 hours, water was added to stop the reaction. The reaction mixture was separated with chloroform added thereto, and the organic layer was dried with magnesium sulfate. The solvent was removed by reduced-pressure distillation, and the residue was purified through silica gel column chromatography (toluene) to give a yellow solid of an intermediate 1 (1.82 g, yield 53%).

¹H NMR (400 MHz, CDCl₃, δ): 8.10 (d, J=8.4 Hz, 1H), 7.99 (d, J=7.6 Hz, 1H), 7.78 (s, 1H), 7.61 (d, J=6.4 Hz, 1H), 7.48-7.40 (m, 4H), 7.36-7.20 (m, 7H), 6.84-6.82 (br, 1H), 6.70 (t, J=7.6 Hz, 1H), 6.40 (t, J=7.6 Hz, 2H), 6.06 (br, 1H).

MS (ASAP): 553.70 [(M+H)⁺, cal. C₃₈H₂₂FN₄, 553.18].

In a nitrogen stream atmosphere, potassium carbonate (0.36 g, 2.6 mmol), benzofuro[2,3-c]carbazole (0.54 g, 2.1 mmol) and the intermediate 1 (0.96 g, 1.7 mmol) were reacted in dimethylformamide (17 mL) at room temperature for 4 hours. Water was added to stop the reaction, and the reaction mixture was separated with chloroform added thereto. The organic layer was dried with magnesium sulfate. The solvent was removed by reduced-pressure distillation, and the residue was purified through silica gel column chromatography (toluene) to give a yellow solid of a compound C4 (1.36 g, yield 99%).

¹H NMR (400 MHz, CDCl₃, δ): 8.78 (s, 1.00), 8.55 (d, J=8.8 Hz, 0.54), 8.27-8.19 (m, 2.38), 8.02-7.97 (m, 1.55), 7.89-7.83 (m, 2.85), 7.94-7.75 (m, 1.99), 7.70-7.62 (m, 1.98), 7.59-7.43 (m, 6.17), 7.39-7.34 (m, 0.51), 7.29-7.26 (m, 2.61), 7.21-7.16 (m, 1.02), 7.06-6.99 (m, 1.00), 6.81 (br, 0.90), 6.67-6.61 (m, 1.00), 6.15 (t, J=7.6 Hz, 0.5), 6.09 (t, J=7.6 Hz, 0.5), 5.91 (br, 1.87), 5.57 (br, 0.90), 5.29 (br, 0.90):

MS (ASAP): 790.31 [(M+H)⁺, cal. C₅₆H₃₂N₄O, 790.25].

(Synthesis Example 5) Synthesis of Compound C5

In a nitrogen stream atmosphere, sodium hydride (0.30 g, 7.5 mmol) and 5-phenyl-5,12-dihydroindolo[3,2-a]carbazole were stirred in THF (50 mL) at room temperature for 1 hour, and then 4,6-difluoro-5-phenylisophthalonitrile (1.49 g, 6.20 mmol) dissolved in THF (50 mL) was dropwise added thereto. After this was reacted for 15 hours at room temperature, water was added to stop the reaction. The reaction mixture was separated with chloroform added thereto, and the organic layer was dried with magnesium sulfate. The solvent was removed by reduced-pressure distillation, and the residue was purified through silica gel column chromatography (toluene) to give a yellow solid of an intermediate 2 (1.70 g, yield 50%).

¹H NMR (400 MHz, CDCl₃, δ): 9.05 (d. J=6.4 Hz, 1H), 8.16 (d, J=8.8 Hz, 1H), 8.09-8.07 (m, 1H), 7.72-7.68 (m, 2H), 7.61-7.57 (m, 3H), 7.37-7.29 (m, 2H), 7.27-7.19 (m, 4H), 7.14-7.02 (m, 2H), 6.99-6.95 (m, 4H), 6.21 (d, J=8.0 Hz, 1H).

MS (ASAP): 553.40 [(M+H)⁺, cal. C₃₈H₂₂FN₄, 553.18].

In a nitrogen stream atmosphere, potassium carbonate (0.43 g, 3.1 mmol), benzofuro[2,3-c]carbazole (0.66 g, 2.6 mmol) and the intermediate 2 (1.30 g, 2.4 mmol) were reacted in dimethylformamide (25 mL) at room temperature for 4 hours. Water was added to stop the reaction, and the reaction mixture was separated with chloroform added thereto. The organic layer was dried with magnesium sulfate. The solvent was removed by reduced-pressure distillation, and the residue was purified through silica gel column chromatography (toluene) to give a yellow solid of a compound C5 (1.63 g, yield 88%).

¹H NMR (400 MHz, CDCl₃, δ): 9.44 (s, 1H), 8.22-8.17 (m, 1H), 8.12-8.07 (m, 1H), 7.76 (d, J=8.0 Hz, 1H), 7.69-7.26 (m, 17H), 7.08 (d, J=8.4 Hz, 1H), 6.54-6.49 (m, 1H), 6.40-6.03 (m, 5H).

MS (ASAP): 790.37 [(M+H)⁺, cal. C₅₆H₃₂N₄O, 790.25].

(Synthesis Example 6) Synthesis of Compound C6

In a nitrogen stream atmosphere, potassium phosphate (1.74 g, 8.2 mmol), 5-phenyl-5,12-dihydroindolo[3,2-a]carbazole (2.28 g, 6.8 mmol) and 4,6-difluoro-5-phenylisophthalonitrile (0.66 g, 2.7 mmol) were reacted in dimethylformamide (30 mL) at 110° C. for 6 hours. After the reaction, water was added to stop the reaction, and the reaction mixture was separated with chloroform added thereto. The organic layer was dried with magnesium sulfate. The solvent was removed by reduced-pressure distillation, and the residue was purified through silica gel column chromatography (toluene) to give a yellow solid of a compound C6 (0.97 g, yield 41%).

¹H NMR (400 MHz, CDCl₃, δ); 9.57 (s, 1H), 8.01 (d, J=7.6 Hz, 2H), 7.91 (d. J=8.4 Hz, 2H), 7.64-7.60 (m, 4H), 7.54-7.50 (m, 4H), 7.42-7.35 (m, 10H), 7.26 (t, J=8.0 Hz, 2H), 7.22-7.19 (m, 2H), 6.91 (d, J=8.4 Hz, 2H), 6.52-6.49 (m, 2H), 6.21 (t, J=7.2 Hz, 1H), 5.78 (t, J=8.0 Hz, 2H), 5.22 (d, J=7.6 Hz, 2H).

MS (ASAP): 865.47 [(M+H)⁺, cal. C₆₂H₃₇N₆, 865.30].

(Synthesis Example 7) Synthesis of Compound C7

In a nitrogen stream atmosphere, sodium hydride (0.19 g, 4.7 mmol), and benzofuro[3,2-c]carbazole (1.02 g, 4.0 mmol) were stirred in tetrahydrofuran (15 mL) at 0° C. for 30 minutes, and then 4,6-difluoro-5-phenylisophthalonitrile was added. The reaction solution was heated up to 40° C. and reacted for 6 hours, and then restored to room temperature, and water and methanol were added to stop the reaction. The precipitated yellow solid was filtered out, and the filtered residue was purified through silica gel column chromatography (toluene/hexane=4/1) and reprecipitation (toluene/methanol) to give a yellow solid of a compound C7 (0.98 g, yield 78%).

¹H NMR (400 MHz, CDCl₃, δ): 8.44 (d, J=8.0 Hz, 2H), 7.99-7.95 (m, 4H), 7.89-7.86 (m, 2H), 7.73-7.63 (m, 5H), 7.49-7.45 (m, 4H), 7.42-7.37 (m, 4H), 7.25 (d, J=8.4 Hz, 2H), 7.23 (d, J=8.8 Hz, 2H), 6.56-6.50 (m, 3H), 6.40 (t, J=7.6 Hz, 2H).

MS (ASAP): 791.26 (M+H⁺). Calcd for C₅₆H₃₀N₄O₂: 790.24

(Synthesis Example 8) Synthesis of Compound C8

In a nitrogen stream atmosphere, sodium hydride (0.49 g, 11.8 mmol), and benzofuro[3,2-c]carbazole (2.54 g, 9.9 mmol) were stirred in tetrahydrofuran (20 mL) at 0° C. for 30 minutes, and then 4,5-difluoro-6-phenylisophthalonitrile was added. The reaction solution was restored to room temperature and reacted for 6 hours at room temperature, and then water and methanol were added to stop the reaction. The precipitated yellow solid was filtered out, and the filtered residue was purified through silica gel column chromatography (toluene/chloroform=10/1) and reprecipitation (toluene/methanol) to give a yellow solid of a compound C8 (0.48 g, yield 17%).

¹H NMR (400 MHz, CDCl₃, δ): (With the presence of stereoisomers in the sample, the proton number is displayed as a relative ratio.) 8.53 (s, 1H), 8.12 (t, J=7.6 Hz, 1H), 7.97-7.94 (m, 1H), 7.89-7.74 (m, 2H), 7.67 (d, J=8.4 Hz, 0.5H), 7.59-7.50 (m, 3H), 7.45 (d, J=8.4 Hz, 0.5H), 7.41-7.28 (m, 4H), 7.22-7.17 (m, 0.5H), 7.14-6.97 (m, 10H), 6.90-6.84 (m, 2.5H).

MS (ASAP): 715.38 (M+H⁺). Calcd for C₅₀H₂₆N₄O₂: 714.21

(Synthesis Example 9) Synthesis of Compound C9

In a nitrogen stream atmosphere, cesium carbonate (1.30 g, 4.0 mmol), 5-phenyl-5,11-dihydroindolo[3,2-a]carbazole (0.78 g, 2.3 mmol) and 4,6-difluoro-5-phenylisophthalonitrile (0.24 g, 1.0 mmol) were reacted in dimethylformamide (20 mL) at 80° C. for 12 hours. After the reaction, water was added at room temperature to stop the reaction, and the reaction mixture was separated with chloroform added thereto. The organic layer was dried with magnesium sulfate. The solvent was removed by reduced-pressure distillation, and the residue was purified through silica gel column chromatography (toluene) and reprecipitation (toluene/methanol) to give a yellow solid of a compound C9 (0.17 g, yield 22%).

¹H NMR (400 MHz, CDCl₃, δ): 8.53 (d. J=7.6 Hz, 1H), 8.21 (d, J=8.0 Hz, 1H), 8.15 (d, J=8.0 Hz, 1H), 7.89-7.96 (m, 4H), 7.85 (s, 1H), 7.78 (s, 1H), 7.07-7.66 (m, 22H), 6.95 (d, J=8.0 Hz, 1H), 6.40-6.58 (m, 3H), 6.34 (t, J=8.0 Hz, 2H).

MS (ASAP): 865.58 (M+H⁺). Calcd for C₆₂H₃₆N₆: 864.30

(Synthesis Example 10) Synthesis of Compound C10

A compound C10 was synthesized according to the same method as in Synthesis Example 1 (yield 84%).

¹H NMR (400 MHz, CDCl₃, δ): 8.62 (s, 2H), 8.51 (s, 1H), 7.99-7.90 (m, 4H), 7.79-7.71 (m, 6H), 7.69-7.64 (m, 2H), 7.52-7.44 (m, 6H), 7.39-7.35 (m, 4H), 7.21-7.18 (m, 2H), 7.09-7.06 (m, 2H), 6.58-6.50 (m, 3H), 6.41 (t, J=8.4 Hz, 2H).

MS (ASAP): 867.50 (M+H⁺). Calcd for C₆₂H₃₄N₄O₂: 866.27.

(Synthesis Example 11) Synthesis of Compound C11

A compound C11 was synthesized according to the same method as in Synthesis Example 1 (yield 78%).

¹H NMR (400 MHz, CDCl₃, δ): 8.62 (s, 2H), 8.51 (s, 1H), 7.96-7.91 (m, 4H), 7.72 (d, J=8.2 Hz, 2H), 7.70-7.64 (m, 2H), 7.46-7.37 (m, 2H), 7.21-7.19 (m, 2H), 7.09-7.06 (m, 2H),

MS (ASAP): 882.21 (M+H⁺). Calcd for C₆₂H₁₉D₁₅N₄O₂: 881.36.

(Synthesis Example 12) Synthesis of Compound C12

A compound C12 was synthesized according to the same method as in Synthesis Example 1 (yield 78%).

¹H NMR (400 MHz, DMSO, δ): 9.48 (s, 1H), 8.51 (s, 1H), 8.29 (d. J=8.4 Hz, 4H), 8.19 (d, J=8.4 Hz, 4H), 7.91 (mJ=8.4 Hz, 4H), 7.84 (t, J=6.8 Hz, 4H), 7.45 (t. J=6.8 Hz, 4H), 6.73 (t, J=7.2 Hz, 2H), 6.38 (t, J=7.2 Hz, 3H),

MS (ASAP): 895.35 (M+H⁺). Calcd for C₆₂H₃₀N₄O₄:894.23

(Synthesis Example 13) Synthesis of Compound C13

A compound C13 was synthesized according to the same method as in Synthesis Example 1 (yield 64%).

¹H NMR (400 MHz, CDCl₃, δ): 8.82-8.76 (m, 4H), 8.45 (s, 1H), 7.64-7.32 (m, 22H), 7.21 (d, J=9.2 Hz, 2H), 7.08-7.05 (m, 2H), 6.47-6.44 (m, 3H), 6.32 (t, J=9.2 Hz, 2H).

MS (ASAP): 865.27 (M+H⁺). Calcd for C₆₂H₃₆N₆: 864.30

(Synthesis Example 14) Synthesis of Compound C14

A compound C14 was synthesized according to the same method as in Synthesis Example 1 (yield 47%).

¹H NMR (400 MHz, CDCl₃, δ): 8.47 (s, 1H), 8.19-8.10 (m, 4H), 7.68-7.51 (m, 10H), 7.38-7.26 (m, 6H), 7.20-7.14 (m, 2H), 7.06-6.98 (m, 4H), 6.74 (t, J=7.6 Hz, 2H), 6.47-6.44 (m, 3H), 6.31 (t, J=7.6 Hz, 2H).

MS (ASAP): 865.37 (M+H⁺). Calcd for C₆₂H₃₆N₆: 864.30

Examples 1 to 9, Comparative Examples 1 to 4 Production and Evaluation of Thin Film

On a quartz substrate according to a vacuum evaporation method, the compound C1 and Host 1 were evaporated from different evaporation sources under the condition of a vacuum degree of less than 1×10⁻³ Pa to form a thin film having a thickness of 100 nm in which the concentration of the compound C1 was 20% by mass, and this is a doped thin film of Example 1.

In place of the compound C1, the compounds C2 to C9 were individually used to produce thin films of Examples 2 to 9, respectively. Also using the comparative compound A and PPF and in the same manner, a thin film of Comparative Example 1 was formed. All the compounds used as light emitting materials in Examples and Comparative Examples in the present description were purified by sublimation before use.

The resultant thin films were individually irradiated with 300-nm excitation light, and all the thin films produced photoluminescence. The lifetime (T4) of the delayed fluorescence was derived from the transient decay curve of emission, and based on the lifetime of Comparative Example 1, a relative value to Comparative Example 1 was calculated. The results are as shown in the following Table. It is confirmed that the delayed fluorescence lifetime (T4) of Examples 1 to 9 is short.

TABLE 2 τ_(d) Compound (%) Example 1 Compound C1 25.7 Example 2 Compound C2 16.2 Example 3 Compound C3 23.2 Example 4 Compound C4 19.2 Example 5 Compound C5 39.2 Example 6 Compound C6 41.5 Example 7 Compound C7 43.7 Example 8 Compound C8 36.5 Example 9 Compound C9 9.95 Comparative Comparative 100 Example 1 Compound A

(Examples 10 to 14, Comparative Example 1) Production and Evaluation of Organic Electroluminescent Device

On a glass substrate having, as formed thereon, an anode of indium tin oxide (ITO) having a thickness of 100 nm, thin films were laminated at a vacuum degree of 1×10⁻⁶ Pa in a vacuum evaporation method. First, HATCN was formed on ITO at a thickness of 10 nm, then NPD was formed thereon at a thickness of 30 nm. Next, TrisPCz was formed at a thickness of 10 nm, and Host1 was formed further thereon at a thickness of 5 nm. Next, the compound C1 and Host1 were co-evaporated from different evaporation sources to form a light emitting layer having a thickness of 30 nm. At that time, the concentration of the compound C1 was 35% by weight. On this, SF3TRZ was formed at a thickness of 10 nm, and further on this, SF3TRZ and Liq were co-evaporated from different evaporation sources at a thickness of 30 nm. At that time, SF3TRZ/Liq (by weight) was 7/3. Further, Liq was formed at a thickness of 2 nm, and then aluminum (Al) was evaporated at a thickness of 100 nm to form a cathode. According to the above process, an organic electroluminescent device of Example 10 was produced.

The compound C2, the compound C3, the compound C4 and a comparative compound A were individually used, in place of the compound C1, to produce organic electroluminescent devices of Examples 11 to 14 and Comparative Example 2, respectively.

(Evaluation)

Emission from the organic electroluminescent device of Example 10 was analyzed to measure x and y in the CIE chromaticity coordinate. The results were x=0.26 and y=0.57 and confirmed good chromaticity. Of the organic electroluminescent devices of Example 10 and Comparative Example 2, the time in which the emission intensity at 12.6 mA/cm² lowered to 95% (LT95) was measured. LT95 of Comparative Example 2 was referred to as 1, and based on this, a relative value of Example 10 was calculated. The results are as shown in the following Table. The device lifetime (device durability) of the organic electroluminescent device of Example 10 significantly improved.

TABLE 3 LT95 Compound (relative value) Example 10 Compound C1 54.4 Comparative Comparative 1 Example 2 Compound A

REFERENCE SIGNS LIST

-   1 Substrate -   2 Anode -   3 Hole Injection Layer -   4 Hole Transporting Layer -   5 Light Emitting Layer -   6 Electron Transporting Layer -   7 Cathode 

1. A compound represented by the following general formula (1):

wherein: R represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group bonding via a carbon atom, Ar represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group bonding via a carbon atom, and D¹ and D² each independently represent a donor group, and at least one of them is a hetero ring-condensed carbazol-9-yl group in which the hetero ring and the carbazol can be substituted.
 2. The compound according to claim 1, wherein the compound is represented by the following general formula (2):


3. The compound according to claim 1, wherein the compound is represented by the following general formula (3):


4. The compound according to claim 1, wherein D¹ and D² are the same.
 5. The compound according to claim 1, wherein D¹ and D² are different.
 6. The compound according to claim 1, wherein the hetero ring condensed with the carbazol-9-yl group of the hetero ring-condensed carbazol-9-yl group is a substituted or unsubstituted furan ring, a substituted or unsubstituted thiophene ring, or a substituted or unsubstituted pyrrole ring, and any other ring can be further condensed with the furan ring, the thiophene ring and the pyrrole ring.
 7. The compound according to claim 1, wherein the hetero ring-condensed carbazol-9-yl group has a structure of any of the following:

wherein hydrogen atoms can be substituted, with which, however, any further hetero atom is not condensed.
 8. The compound according to claim 1, wherein the hetero ring-condensed carbazol-9-yl group has a structure of any of the following:

wherein hydrogen atoms can be substituted, with which, however, any further hetero atom is not condensed.
 9. The compound according to claim 1, wherein the hetero ring-condensed carbazol-9-yl group has a structure of any of the following:

wherein hydrogen atoms can be substituted, with which, however, any further hetero atom is not condensed, and R′ represents a hydrogen atom, a deuterium atom or a substituent.
 10. The compound according to claim 1, wherein two hetero rings selected from the group consisting of a substituted or unsubstituted furan ring, a substituted or unsubstituted thiophene ring and a substituted or unsubstituted pyrrole ring, in which any other ring can be condensed with the furan ring, the thiophene ring and the pyrrole ring, are condensed with the carbazol-9-yl group of the hetero ring-condensed carbazol-9-yl group.
 11. The compound according to claim 1, wherein the hetero ring-condensed carbazol-9-yl group has a structure with a hetero ring condensed at 1,2-positions of the carbazole ring.
 12. The compound according to claim 1, wherein the hetero ring-condensed carbazol-9-yl group has a structure with a hetero ring condensed at 2,3-positions of the carbazole ring.
 13. The compound according to claim 1, wherein the hetero ring-condensed carbazol-9-yl group has a structure with a hetero ring condensed at 3,4-positions of the carbazole ring.
 14. The compound according to claim 1, wherein R and Ar differ.
 15. The compound according to claim 1, wherein R is a hydrogen atom or a deuterium atom.
 16. The compound according to claim 1, wherein Ar is a substituted or unsubstituted phenyl group, or a substituted or unsubstituted pyridyl group.
 17. The compound according to claim 1, which is composed of atoms selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, an oxygen atom and a sulfur atom.
 18. (canceled)
 19. A light emitting device containing the compound of claim
 1. 20. The light emitting device according to claim 19, wherein the light emitting device has a light emitting layer and the light emitting layer contains the compound and a host material.
 21. The light emitting device according to claim 20, wherein the light emitting device has a light emitting layer, the light emitting layer contains the compound and a light emitting material, and the light emitting material mainly emits light. 